The Organic Reagent Book

The
organic chemistry
Reagent
Book
@bohring_bot
Index Index
4 5
Index Index
Reagents and Solvents End Notes
Ac2O Acetic Anhydride 6 HgSO4 Mercuric Sulfate 54 NMO NÐmethylmorpholine Common Abbreviations & Terms 134
AgNO3 Silver Nitrate 7 HI Hydroiodic acid 55 1R[LGH Functional Groups 135
Ag2O Silver Oxide 8 HIO4 Periodic acid 57 O3 2]RQH pKas of Common Functional Groups
$,%1 >·$]RELV PHWK\O +212 1LWURXV$FLG +122) 58 R2CuLi Organocuprates 104 136
propionitrile)] 9 HNO3 Nitric Acid 59 RLi Organolithium reagents 105 Notes on Acids 138
AlBr3 Aluminum bromide 10 H2O2 Hydrogen peroxide 60 OsO4 Osmium tetroxide 108 Notes on Bases 140
AlCl3 Aluminum chloride 11 H3PO4 Phosphoric acid 62 3E 2$F 4 Lead tetraacetate 109 2[LGL]LQJ$JHQWV
BF3 %RURQ7ULÁXRULGH H2SO4 Sulfuric acid 63 PBr3 Phosphorus tribromide 110 Reducing Agents 143
BH3 Borane 14 I2 Iodine 64 PCl3 Phosphorus trichloride 111 Organometallic Reagents 145
Br2 Bromine 16 KMnO4 Potassium permanganate 66 PCl5 Phosphorus Pentachloride 112 Reagents for Making Alkyl/Acyl
BsCl pEURPREHQ]HQH KCN Potassium cyanide 23 P2O5 Phosphorus pentoxide 113 Halides 147
sulfonyl chloride 19 KOt%X 3RWDVVLXPtEXWR[LGH Pd/C Palladium on carbon 114 Reagents Involving Aromatic Rings
CCl4 Carbon Tetrachloride 151 KPhth Potassium Phthalimide 70 3G 33K3)4Palladium ÒtetrakisÓ 155 148
CH2Cl2 Dichloromethane 151 LDA Lithium diisopropyl amide 71 Pt Platinum 115 Types of Arrows 150
Cl2 Chlorine 20 Li Lithium 72 PCC Pyridinium chlorochromate 116 Types of Solvents 151
CN Cyanide ion 23 /LQGODU·V&DWDO\VW POCl3 Phosphorus oxychloride 117 Protecting Groups 152
CrO3 Chromium trioxide 24 LiAlH4 Lithium aluminum hydride 75 PPh3 Triphenylphosphine 118 2OHÀQ0HWDWKHVLV
&X%U &RSSHU , %URPLGH /L$O+ 2t-Bu)3 /LWKLXPWULWHUWEXWR[\ Pyridine 119 Cross Coupling Reagents 155
&X&O &RSSHU , &KORULGH aluminum hydride 77 RaÐNi Raney Nickel 120
&X, &RSSHU , ,RGLGH m&3%$m-chloroperoxy ROÐOR Peroxides 121
D Deuterium 32 EHQ]RLFDFLG SO3 Sulfur trioxide 122
'%8 'LD]RELF\FOR Mg Magnesium 80 SOBr2 Thionyl bromide 123
XQGHFHQH MsCl Methanesulfonyl chloride 81 SOCl2 Thionyl chloride 124
DCC N,N·GLF\FORKH[DQH NaN3 6RGLXPD]LGH Sn Tin 125
carbodiimide 29 Na Sodium 83 TBAF Tetrabutyl ammonium
CH2N2 'LD]RPHWKDQH NaBH4 Sodium borohydride 85 ÁXRULGH
',%$/ 'LLVREXW\ODOXPLQXP 1D%+ 2$F 3 Sodium triacetoxy THF Tetrahydrofuran 151
hydride 33 borohydride 87 TMSCl Trimethylsilyl chloride 127
'0) 11·'LPHWK\OIRUPDPLGH NaCNBH3 Sodium TsCl p7ROXHQHVXOIRQ\O
'03 'HVV0DUWLQ3HULRGLQDQH cyanoborohydride 88 chloride 128
'06 'LPHWK\OVXOÀGH Na2Cr2O7 Sodium dichromate 50 TsOH p7ROXHQHVXOIRQLFDFLG
DMSO Dimethyl sulfoxide 151 NaH Sodium Hydride 89 Zn Zinc 130
Et2O Diethyl ether 151 NaIO4 Sodium periodate 90 =Q&X =LQF&RSSHU&RXSOH
Fe Iron 36 NaNO2 Sodium nitrite 58 =Q +J =LQFDPDOJDP
FeBr3 ,URQ ,,, EURPLGHCCCCC NaNH2 Sodium amide 91 Odds And Ends 133
FeCl3 ,URQ ,,, FKORULGH NaOH Sodium hydroxide 92
Grignard Reagents 40 NaOEt Sodium Ethoxide 93
*UXEEV·&DWDO\VW NBS NÐBromosuccinimide 94
H2 Hydrogen 43 NCS NÐChloro Succinimide 96
H+ Anhydrous Acid 44 NIS NÐIodo Succinimide 97
H3O+ Aqueous acid 45 NH2OH Hydroxylamine 98
HBr Hydrobromic acid 46 NH3 Ammonia 99
HCl Hydrochloric acid 48 NH2NH2 +\GUD]LQH
H2CrO4 Chromic acid 50 Ni2B Nickel boride 101
+J 2$F 2 Mercuric Acetate 52
Organic Chemistry Reagent Guide @bohring_bot
Index http://masterorganicchemistry.com Index
Index Index
6 7
(N563
Ac2O :PS]LY5P[YH[L
Acetic Anhydride
:KDWLW·VXVHGIRU6LOYHUQLWUDWHZLOOUHDFWZLWKDON\OKDOLGHVWRIRUPVLOYHUKDOLGHV
DQGWKHFRUUHVSRQGLQJFDUERFDWLRQ:KHQDQXFOHRSKLOLFVROYHQWVXFKDVZDWHU
:KDWLW·VXVHGIRU&RQYHUWVDOFRKROVWRDFHWDWHV HVWHUV &DQEHXVHGDVD RUDQDOFRKROLVXVHGWKLVFDQUHVXOWLQDQ6NUHDFWLRQ,WFDQDOVRUHDFWLQWKH
WHPSRUDU\SURWHFWLQJJURXSIRUDOFRKROVHVSHFLDOO\ZLWKVXJDUV8VHGWRFRQYHUW 7ROOHQVUHDFWLRQWRJLYHFDUER[\OLFDFLGVIURPDOGHK\GHV
Similar to: $J%)4
FDER[\OLFDFLGVWRDQK\GULGHV&DQDOVREHXVHGLQWKH)ULHGHO&UDIWVDF\ODWLRQRI
([DPSOH6XEVWLWXWLRQ 6N1) conversion of alkyl halides to alcohols
DURPDWLFULQJV
Example 1: Acetylation of alcohols
([DPSOH6XEVWLWXWLRQ 6N1) conversion of alkyl halides to ethers
Example 2: Conversion of carboxylic acids to anhydrides ([DPSOH7ROOHQVR[LGDWLRQFRQYHUVLRQRIDOGHK\GHVWRFDUER[\OLFDFLGV
How it works: SN1 Reaction of alkyl halides

([DPSOH)ULHGHO&UDIWVDF\ODWLRQ
6LOYHUQLWUDWH$J123KDVJRRGVROXELOLW\LQDTXHRXVVROXWLRQEXW$J%U$J&ODQG$J,
GRQRW$JFRRUGLQDWHVWRWKHKDOLGHZKLFKWKHQOHDYHVIRUPLQJDFDUERFDWLRQ7KH
Many other catalysts FDUERFDWLRQLVWKHQWUDSSHGE\VROYHQW OLNH+2
besides AlCl3 can be used
(e.g. BF3, FeCl3)
How it works: Friedel-Crafts Acylation
$FLGKDOLGHVDUHPRVWRIWHQXVHGIRUWKH)ULHGHO&UDIWVDF\ODWLRQEXWDQK\GULGHV
VXFKDV$F2PD\EHXVHGDVZHOO$O&O3LVVKRZQDVWKH/HZLVDFLGEXWPDQ\
RWKHU/HZLVDFLGVZRUNZHOO
Activation of Ac2O Acylium ion

with Lewis acid (reactive intermediate)
Attack of aromatic ring on Re-aromatization (often shown

acylium ion electrophile with generic base B3 )
Index Index
8 9
(0)5
Ag2O
:PS]LY6_PKL Tdorf B»(aVIPZTL[O`S
WYVWPVUP[YPSLD
:KDWLW·VXVHGIRU6LOYHUR[LGHLVXVHGLQWKH7ROOHQVUHDFWLRQWRR[LGL]HDOGHK\GHV
WRFDUER[\OLFDFLGV7KLVLVWKHEDVLVRIDWHVWIRUWKHSUHVHQFHRIDOGHK\GHVVLQFHD
PLUURURI$JRZLOOEHGHSRVLWHGRQWKHÁDVN,WLVDOVRXVHGDVWKHEDVHLQWKH+RIIPDQ :KDWLW·VXVHGIRU)UHHUDGLFDOLQLWLDWRU8SRQKHDWLQJ$,%1GHFRPSRVHVWR
HOLPLQDWLRQ JLYHQLWURJHQJDVDQGWZRIUHHUDGLFDOV
Similar to: $J123 Similar to: 52²25 ´SHUR[LGHVµ EHQ]R\OSHUR[LGH

Example 1: Tollens oxidation of aldehydes to carboxylic acids
([DPSOH)UHHUDGLFDOKDORJHQDWLRQRIDONHQHV
How it works: Free-radical halogenation of alkenes

This reaction is usually
$OGHK\GH RSHQIRUP
introduced in the con-
text of sugar chemistry
Example 2: As the base in the Hoffmann elimination

f
10
(S)Y3
(S\TPU\T)YVTPKL
Index
I
Index
(S*S3
(S\TPU\TJOSVYPKL
11
Also known as:$OXPLQXPWULEURPLGH Also known as:$OXPLQXPWULFKORULGH
:KDWLW·VXVHGIRU/HZLVDFLGSURPRWHUIRUHOHFWURSKLOLFDURPDWLFVXEVWLWXWLRQ :KDWLW·VXVHGIRU$OXPLQXPFKORULGHLVDVWURQJ/HZLVDFLG,WFDQEHXVHGWR
FDWDO\]HWKHFKORULQDWLRQRIDURPDWLFFRPSRXQGVDVZHOODV)ULHGHO&UDIWVUHDF-
WLRQV,WFDQDOVREHXVHGLQWKH0HHUZHLQ3RQQGRUI9HUOH\UHGXFWLRQ
Similar to: )H&O3)H%U3$O&O3
Similar to:$O%U3)H%U3)H&O3
([DPSOH(OHFWURSKLOLFFKORULQDWLRQFRQYHUVLRQRIDUHQHVWRDU\OKDOLGHV
([DPSOH(OHFWURSKLOLFEURPLQDWLRQFRQYHUVLRQRIDUHQHVWRDU\OKDOLGHV
([DPSOH)ULHGHO&UDIWVDF\ODWLRQFRQYHUVLRQRIDUHQHVWRDU\ONHWRQHV
([DPSOH)ULHGHO&UDIWVDON\ODWLRQFRQYHUVLRQRIDUHQHVWRDON\ODUHQHV
([DPSOH0HHUZHLQ3RQQGRUI9HUOH\UHGXFWLRQUHGXFWLRQRINHWRQHVDQG
alcohols to aldehydes
How it works: Friedel-Crafts acylation

Index Index
12 13
(S*S3 BF3
JVU[PU\LK )VYVU;YPÅ\VYPKL
How it works: Meerwein-Ponndorf-Verley Oxidation :KDWLW·VXVHGIRU%RURQWULÁXRULGHLVDVWURQJ/HZLVDFLG,WLVFRPPRQO\XVHG

IRUWKHIRUPDWLRQRIWKLRDFHWDOVIURPNHWRQHV RUDOGHK\GHV ZLWKWKLROV7KHSURG-
7KLVUHDFWLRQLVW\SLFDOO\UXQXVLQJDQDOFRKROVROYHQWVXFKDVHWKDQRORULVR- XFWLVDWKLRDFHWDO
SURSDQRO:KHQ$O&O3LVDGGHGWKHVROYHQWUHSODFHVWKHFKORURJURXSV
Similar to:)H&O3$O&O3 DOVR/HZLVDFLGV
Example 1: Conversion of ketones to thioacetals
How it works: Formation of thioacetals

%)3DFWVDVD/HZLVDFLGFRRUGLQDWLQJWRWKHFDUERQ\OR[\JHQDQGDFWLYDWLQJWKH
FDUERQ\OFDUERQWRZDUGVDWWDFNE\VXOIXU
Coordination Addition
Proton transfer
Addition
Elimination
This is the key step. Note how the
ketone is reduced to a secondary
alcohol and the alcohol is oxidized.
Deprotonation
The aluminum alkoxide can go on to

catalyze further reactions.

Index Index
14 15
BH3 BH3
Borane JVU[PU\LK
:KDWLW·VXVHGIRU%RUDQHLVXVHGIRUWKHK\GURERUDWLRQRIDONHQHVDQGDON\QHV 7KHVHFRQGVWHSRIWKHK\GURERUDWLRQLVDQR[LGDWLRQWKDWUHSODFHVWKH&²%ERQGZLWK
D&²2ERQG
Similar to:%+6 ´GLERUDQHµ %+37+)%+360HGLVLDP\OERUDQH%%1 IRU
RXUSXUSRVHVWKHVHFDQDOOEHFRQVLGHUHGDV´LGHQWLFDOµ
([DPSOH+\GURERUDWLRQUHDFWLRQFRQYHUVLRQRIDONHQHVWRDOFRKROV
7KHÀUVWVWHSLVGHSURWRQDWLRQRIK\GURJHQSHUR[LGHE\VRGLXPK\GUR[LGHWKLVPDNHV
WKHSHUR[LGHLRQPRUHQXFOHRSKLOLF DQGPRUHUHDFWLYH
7KHGHSURWRQDWHGSHUR[LGHWKHQDWWDFNVWKHERURQZKLFKWKHQXQGHUJRHVUHDUUDQJH-
PHQWWREUHDNWKHZHDN2²2ERQG7KHQK\GUR[LGHLRQFOHDYHVWKH%²2ERQGWR
([DPSOH+\GURERUDWLRQUHDFWLRQFRQYHUVLRQRIDON\QHVWRDOGHK\GHV JLYHDGHSURWRQDWHGDOFRKROZKLFKLVWKHQSURWRQDWHGE\DOFRKRO
How it works: Hydroboration of alkenes How it works: Hydroboration of alkynes

+\GURERUDWLRQLVQRWDEOHLQWKDWWKHboron adds to the less substituted end of +\GURERUDWLRQRIDON\QHVIRUPVDSURGXFWFDOOHGDQenol7KURXJKDSURFHVVFDOOHG
the alkene7KLVLVXVXDOO\UHIHUUHGWRDV´DQWL0DURYQLNRIIµVHOHFWLYLW\7KHUHDVRQ tautomerismWKHHQROSURGXFWLVFRQYHUWHGLQWRLWVPRUHVWDEOHFRQVWLWXWLRQDOLVRPHU
IRUWKHVHOHFWLYLW\LVWKDWWKHERURQK\GURJHQERQGLVSRODUL]HGVRWKDWWKH WKHketoIRUP,QWKHFDVHRIDWHUPLQDODON\QH RQHZKLFKKDVD&+ERQG DQDOGH-
hydrogen has a partial negative charge and the boron has a partial positive K\GHLVIRUPHG
FKDUJH GXHWRHOHFWURQHJDWLYLW\ ,QWKHWUDQVLWLRQVWDWHthe partially negative
hydrogen Òlines upÓ with the more substituted end of the double bond LH
WKHHQGFRQWDLQLQJPRUHERQGVWRFDUERQ VLQFHWKLVZLOOSUHIHUHQWLDOO\VWDELOL]H
SDUWLDOSRVLWLYHFKDUJH7KHK\GURJHQDQGERURQDGGsynWRWKHGRXEOHERQG

Index Index
16 17
Br2 Br2
Bromine JVU[PU\LK
:KDWLW·VXVHGIRU%URPLQHZLOOUHDFWZLWKDONHQHVDON\QHVDURPDWLFVHQROVDQG ([DPSOH5DGLFDOKDORJHQDWLRQFRQYHUVLRQRIDONDQHVWRDON\OEURPLGHV
HQRODWHVSURGXFLQJEURPLQDWHGFRPSRXQGV,QWKHSUHVHQFHRIOLJKWEURPLQHZLOO
DOVRUHSODFHK\GURJHQDWRPVLQDONDQHV)LQDOO\EURPLQHLVDOVRXVHGWRSURPRWH
WKH+RIIPDQQUHDUUDQJHPHQWRIDPLGHVWRDPLQHV
([DPSOH+DORIRUPUHDFWLRQFRQYHUVLRQRIPHWK\ONHWRQHVWRFDUER[\OLF
Similar to:1%6&O,1,61&6 acids
([DPSOH%URPLQDWLRQFRQYHUVLRQRIDONHQHVWRYLFLQDOGLEURPLGHV
How it works: Bromination of alkenes

([DPSOH%URPLQDWLRQFRQYHUVLRQRIDON\QHVWRYLFLQDOGLEURPLGHV
Example 3: Conversion of alkenes to halohydrins
7UHDWPHQWRIDQDONHQHZLWK%UOHDGVWRWKHIRUPDWLRQRIDEURPRQLXPLRQZKLFK
XQGHUJRHVEDFNVLGHDWWDFN,QWKHSUHVHQFHRIDVROYHQWWKDWFDQDFWDVDQXFOHR
([DPSOH(OHFWURSKLOLFEURPLQDWLRQFRQYHUVLRQRIDUHQHVWRDU\OEURPLGHV
SKLOHWKHKDORK\GULQLVREWDLQHG
([DPSOH+RIIPDQQUHDUUDQJHPHQWFRQYHUVLRQRIDPLGHVWRDPLQHV
How it works: Bromination of alkenes
%URPLQHLVPDGHPRUHHOHFWURSKLOLFE\D/HZLVDFLGVXFKDV)H%U3LWFDQWKHQ
XQGHUJRDWWDFNE\DQDURPDWLFULQJUHVXOWLQJLQHOHFWURSKLOLFDURPDWLFVXEVWLWXWLRQ
Example 6: Conversion of ketones to _EURPRNHWRQHV RI+IRU%U
Example 7: Conversion of enolates to _EURPRNHWRQHV

Index Index
18 19
Br2 )Z*S
JVU[PU\LK pIYVTVILUaLULZ\SMVU`S
JOSVYPKL
How it works: Hoffmann Rearrangement
In this reaction, the lone pair on nitrogen attacks bromine, which leads to a re- Also known as:%URV\OFKORULGH
arrangement. Attack at the carbonyl carbon by water then leads to loss of CO2,
resulting in the formation of the free amine. :KDWLW·VXVHGIRUpEURPREHQ]HQHVXOIRQ\OFKORULGH %V&O LVXVHGWRFRQYHUW
DOFRKROVLQWRJRRGOHDYLQJJURXSV,WLVHVVHQWLDOO\LQWHUFKDQJDEOHZLWK7V&ODQG
0V&OIRUWKLVSXUSRVH
Similar to: 7V&O0V&O
Example 1: Conversion of alcohols into alkyl brosylates
Attack
Bromination Rearrangement by H2O
Loss of CO2
How it works: Bromination of enols
How it works: Bromination of enolates
How it works: Halogenation of alkanes

Index Index
20 21
*S2 *S2
*OSVYPUL JVU[PU\LK
:KDWLW·VXVHGIRU&KORULQHLVDYHU\JRRGHOHFWURSKLOH,WZLOOUHDFWZLWKGRXEOH Example 8: The haloform reaction

DQGWULSOHERQGVDVZHOODVDURPDWLFVHQROVDQGHQRODWHVWRJLYHFKORULQDWHG
SURGXFWV,QDGGLWLRQLWZLOOVXEVWLWXWH&OIRUKDORJHQVZKHQWUHDWHGZLWKOLJKW
IUHHUDGLFDOFRQGLWLRQV )LQDOO\LWDVVLVWVZLWKWKHUHDUUDQJHPHQWRIDPLGHVWR
DPLQHV WKH+RIIPDQQUHDUUDQJHPHQW
Similar to:1&6%U1%6I1,6 How it works: Chlorination of alkenes
Note how the anti product is
([DPSOH&KORULQDWLRQFRQYHUVLRQRIDONHQHVWRYLFLQDOGLFKORULGHV formed exclusively, through
backside attack on the
chloronium ion
Example 2: Conversion of alkenes to chlorohydrins

How it works: Chlorohydrin formation
([DPSOH(OHFWURSKLOLFFKORULQDWLRQFRQYHUVLRQRIDUHQHVWRFKORURDUHQHV
In a nucleophilic solvent such as H2O, water will attack the

chloronium ion, forming a chlorohydrin
How it works: Electrophilic chlorination
([DPSOH+RIIPDQQUHDUUDQJHPHQWFRQYHUVLRQRIDPLGHVWRDPLQHV
*OUIFmSTUTUFQPGUIJTSFBDUJPO
a Lewis acid such as FeCl3 acti-
vates Cl2 towards attack by the
aromatic ring.
Example 5: Conversion of ketones to _FKORURNHWRQHV
Example 6: Conversion ot enolates to _FKORURNHWRQHV

In the second step, electrophilic aromatic substitution
results in replacement of C3H by C-Cl
How it works: Chlorination of ketones under acidic conditions

Example 7: Radical chlorination of alkanes to alkyl chlorides

Index Index
22 23
*S2 *5
JVU[PU\LK Cyanide ion
How it works: Chlorination of enolates :KDWLW·VXVHGIRU&\DQLGHLRQLVDJRRGQXFOHRSKLOH,WFDQEHXVHGIRUVXEVWL-

WXWLRQUHDFWLRQV 6N IRUIRUPLQJF\DQRK\GULQVIURPDOGHK\GHVRUNHWRQHVDQGLQ
WKHEHQ]RLQFRQGHQVDWLRQ
Same as: .&11D&1/L&1

Example 1: As a nucleophile in substitution reactions
Deprotonation of the ketone by strong base
results in an enolate, which then attacks Cl2
Example 2: Formation of cyanohydrins from aldehydes/ketones
How it works: Chlorination of alkanes
([DPSOH,QWKHEHQ]RLQFRQGHQVDWLRQ
How it works: Nucleophilic substitution
Cyanide ion is a good

nucleophile but a
weak base (pKa of 9)
How it works: Hoffmann Rearrangement
How it works: Benzoin condensation
Carbonyl
addition
Here, the proton is transferred
betweeen carbon and oxygen
Expulsion
of cyanide

Index Index
24 25
CrO3 CrO3
Chromium trioxide JVU[PU\LK
:KDWLW·VXVHGIRU&U23LVDQR[LGDQW:KHQS\ULGLQHLVSUHVHQWLWLVDPLOGR[- How it works: Oxidation of primary alcohols to carboxylic acids

LGDQWWKDWZLOOR[LGL]HSULPDU\DOFRKROVWRDOGHK\GHV+RZHYHULIZDWHUDQGDFLG
:KHQZDWHULVSUHVHQWWKHDOGHK\GHZLOOIRUPWKHK\GUDWHZKLFKZLOOEHIXUWKHU
DUHSUHVHQWWKHDOGHK\GHZLOOEHR[LGL]HGIXUWKHUWKHWKHFDUER[\OLFDFLG
R[LGL]HGWRWKHFDUER[\OLFDFLG
Similar to:3&& ZKHQS\ULGLQHLVDGGHG
When aqueous acid is presentLWLVWKHVDPHRUVLPLODUWR1D&U24.&U27
1D&U27+&U24 DQG.0Q24 :DWFKRXWWKLVUHDJHQWLVWKHVRXUFHRIPXFK
FRQIXVLRQ
([DPSOH2[LGDWLRQRISULPDU\DOFRKROVWRDOGHK\GHV ZLWKS\ULGLQH
Hydrate
Water is a strong enough base to
deprotonate here
([DPSOH2[LGDWLRQRIVHFRQGDU\DOFRKROVWRNHWRQHV ZLWKS\ULGLQH
After proton transfer Second deprotonation results in

formation of the carbonyl
Example 3: Oxidation of primary alcohols to carboxylic acids
How it works: Oxidation of primary alcohols to aldehydes
proton transfer
pyridine (a base)

Index Index
26 27
CuBr *\*S
*VWWLY0)YVTPKL *VWWLY0*OSVYPKL
Also known as:&XSURXVEURPLGH Also known as:&XSURXVFKORULGH

:KDWLW·VXVHGIRU5HDFWVZLWKDURPDWLFGLD]RQLXPVDOWVWRJLYHDURPDWLFEUR- :KDWLW·VXVHGIRU5HDFWVZLWKDURPDWLFGLD]RQLXPVDOWVWRJLYHDU\OFKORULGHVDOVR
PLGHV$OVRXVHGWRPDNHRUJDQRFXSUDWHV *LOPDQUHDJHQWV XVHGWRIRUPRUJDQRFXSUDWHV *LOPDQUHDJHQWV IURPRUJDQROLWKLXPVDOWV
Similar to:&RSSHU , F\DQLGH &X&1 &RSSHU , FKORULGH&RSSHU , LRGLGH Similar to: &RSSHU , F\DQLGH &X&1 &RSSHUEURPLGH&RSSHU,RGLGH
([DPSOH)RUPDWLRQRIDU\OEURPLGHVIURPDU\OGLD]RQLXPVDOWV ([DPSOH)RUPDWLRQRIDU\OFKORULGHVIURPGLD]RQLXPVDOWV
([DPSOH)RUPDWLRQRIRUJDQRFXSUDWHUHDJHQWV *LOPDQUHDJHQWV ([DPSOH)RUPDWLRQRIRUJDQRFXSUDWHV *LOPDQUHDJHQWV
How it works: Formation of aryl bromides How it works: Formation of aryl chlorides from aryl diazonium salts
1RWSHUIHFWO\XQGHUVWRRG 1RWSHUIHFWO\XQGHUVWRRGDOWKRXJKSURFHHGVWKURXJKDIUHHUDGLFDOSURFHVV
,WLVNQRZQWKDWWKLVUHDFWLRQRFFXUVWKURXJKDIUHHUDGLFDOSURFHVV+HUHLVD 6XJJHVWHGPHFKDQLVP
VXJJHVWHGPHFKDQLVP
Donation of an electron by Donation of an electron by
Cu(I) to give Cu(II) Cu(I) to give Cu(II)
Driving force for this reac- Driving force for this reac-
tion is loss of nitrogen gas! tion is loss of nitrogen gas!
The radical then abstracts Br The radical then abstracts Cl

from CuBr2,, giving CuBr from CuCl2,, giving CuCl

Index Index
28 29
CuI DCC
*VWWLY00VKPKL N,N»KPJ`JSVOL_HUL
JHYIVKPPTPKL
Also known as:&XSURXVLRGLGH :KDWLW·VXVHGIRU'&&LVSULPDULO\XVHGIRUWKHV\QWKHVLVRIDPLGHVIURPDPLQHV
DQGFDUER[\OLFDFLGV,WLVHVVHQWLDOO\DGHK\GUDWLRQUHDJHQW UHPRYHVZDWHU
:KDWLW·VXVHGIRU5HDFWVZLWKDON\OOLWKLXPUHDJHQWVWRIRUPGLDON\OFXSUDWHV
Similar to:&X%U&X&1&X&O
([DPSOH)RUPDWLRQRIGLDON\OFXSUDWHV *LOPDQUHDJHQWV Example 1: Formation of amides from carboxylic acids and amines
How it works: Formation of organocuprates
How it works: Formation of amides from carboxylic acids and amines

7KHÀUVWVWHSLVDWWDFNRIWKHFDUERQRQWKHLPLGHE\WKHR[\JHQRQWKHFDUER[\OLF
DFLG
Proton transfer
Now the amine
&XSUDWHVFDQEHXVHGWRGRFRQMXJDWHDGGLWLRQV>DGGLWLRQ@
BEE attacks!
7KH\ZLOODOVRDGGWRDF\OKDOLGHVWRJLYHNHWRQHV
Amide
This byproduct is called a <urea=

(formed after proton transfer)

Index Index
30 31
DMS CH252
+PTL[O`SZ\SÄKL +PHaVTL[OHUL
Also known as:0H6PHWK\OVXOÀGH :KDWLW·VXVHGIRU'LD]RPHWKDQHLVXVHGIRUWKUHHPDLQSXUSRVHV WRFRQYHUW

:KDWLW·VXVHGIRU8VHGLQWKHÚHGXFWLYHZRUNXSµRIR]RQRO\VLVWRUHGXFHWKH FDUER[\OLFDFLGVLQWRPHWK\OHVWHUVDQG LQWKH:ROIIUHDUUDQJHPHQWDVDPHDQV
R]RQLGHWKDWLVIRUPHG'06LVR[LGL]HGWRGLPHWK\OVXOIR[LGH '062 LQWKH WRH[WHQGFDUER[\OLFDFLGVE\RQHFDUERQDQG IRUF\FORSURSDQDWLRQRIDONHQHV
SURFHVV
Similar to: =Q LQWKHUHGXFWLYHZRUNXSIRUR]RQRO\VLV Example 1: Conversion of carboxylic acids to methyl esters
([DPSOH5HGXFWLYHZRUNXSIRUR]RQRO\VLV
Example 2: Cyclopropanation of alkenes
How it works: Reductive workup for ozonolysis

7KHÀUVWVWHSLVIRUPDWLRQRIDQR]RQLGHE\WUHDWLQJDQDONHQHZLWK23
Example 3: In the Wolff Rearrangement
How it works: Formation of methyl esters
How it works: Wolff Rearrangement

6WHSLVDGGLWLRQRIGLD]RPHWKDQHWRWKHDFLGFKRULGHDQGGLVSODFHPHQWRI&O
,QWKHVHFRQGVWHSWKHR]RQLGHLVWUHDWHGZLWK'06ZKLFKUHVXOWVLQUHGXFWLRQ Addition
RIWKHR]RQLGHDQGIRUPDWLRQRIGLPHWK\OVXOIR[LGH '062
Eliimination
6WHSLVKHDWZKLFKLQLWLDWHVWKHUHDUUDQJHPHQWIRUPLQJDNHWHQH
DMSO
Heating leads to
loss of N2 gas
,QVWHSDGGLWLRQRIZDWHUIRUPVWKHFDUER[\OLFDFLG
Tautomerism

Index
(after proton transfer)
http://masterorganicchemistry.com Index
Index Index
32 33
D DIBAL
Deuterium +PPZVI\[`SHS\TPU\T
hydride
Also known as:´KHDY\K\GURJHQµ
:KDWLW·VXVHGIRU'HXWHULXPLVWKHKHDY\LVRWRSHRIK\GURJHQKDYLQJDQ :KDWLW·VXVHGIRU6WURQJEXON\UHGXFLQJDJHQW,WLVPRVWXVHIXOIRUWKHUHGXF-
DWRPLFZHLJKWRIWZR'HXWHULXPKDVHVVHQWLDOO\WKHVDPHUHDFWLYLW\DVK\GURJHQ WLRQRIHVWHUVWRDOGHK\GHVXQOLNH/L$O+4LWZLOOQRWUHGXFHWKHDOGHK\GHIXUWKHU
EXWGXHWRWKHGLIIHUHQWPDJQHWLFSURSHUWLHVRIWKHQXFOHXVLWFDQEHGLIIHUHQWLDWHG XQOHVVDQH[WUDHTXLYDOHQWLVDGGHG,WZLOODOVRUHGXFHRWKHUFDUERQ\OFRPSRXQGV
IURPK\GURJHQLQ+105'HXWHULXPDQDORJVRIK\GURJHQFRQWDLQLQJUHDJHQWV VXFKDVDPLGHVDOGHK\GHVNHWRQHVDQGQLWULOHV
FDQWKHUHIRUHEHXVHIXOLQLQWURGXFLQJGHXWHULXPDVDÓDEHOµIRUH[DPLQLQJVWH-
Similar to: /L$O+4 /$+ /L$O+ 2W%X
UHRFKHPLVWU\DQGPHFKDQLVPV 3
Example 1: Deuterium reagents as acids Example 1: Reduction of esters to aldehydes
Low temperature is
important to prevent further
reduction
Example 2: Reduction of ketones to secondary alcohols
Example 2: Hydroboration of alkenes
Example 3: Reduction of aldehydes to primary alcohols
Example 3: Reduction of ketones

Example 4: Reduction of nitriles to aldehydes
The reaction initially forms
an imine, which is then
hydrolyzed by acid
Example 5: Reduction of acyl halides to aldehydes
Low temperature is
important to prevent further
How it works: Deuterium as a reagent
reduction
)RUH[DPSOHVRIWKHPHFKDQLVPVVHHWKHVHFWLRQIRUWKHFRUUHVSRQGLQJ
K\GURJHQUHDJHQWV

Index Index
34 35
DIBAL DMP
JVU[PU\LK Dess-Martin Periodinane
How it works: Reduction of esters to aldehydes
:LWKLWVEXON\LVREXW\OJURXSV',%$/LVPRUHVWHULFDOO\KLQGHUHGWKDQ/L$O+4,I
WKHWHPSHUDWXUHLVNHSWORZ',%$/FDQUHGXFHDQHVWHUWRDQDOGHK\GHZLWKRXW :KDWLW·VXVHGIRU'HVV0DUWLQSHULRGLQDQHLVDQR[LGL]LQJDJHQW,WZLOOR[LGL]H
VXEVHTXHQWUHGXFWLRQWRWKHDOFRKRO SULPDU\DOFRKROVWRDOGHK\GHVZLWKRXWJRLQJWRWKHFDUER[\OLFDFLG VLPLODUWR3&&
,WZLOODOVRR[LGL]HVHFRQGDU\DOFRKROVWRNHWRQHV
Similar to:3&&&U23ZLWKS\ULGLQH
([DPSOH2[LGDWLRQFRQYHUVLRQRISULPDU\DOFRKROVWRDOGHK\GHV
([DPSOH2[LGDWLRQFRQYHUVLRQRIVHFRQGDU\DOFRKROVWRNHWRQHV
5IFmSTUTUFQ Next, hydride is At low tempera-
is coordination delivered to the tures the product
of the oxygen carbonyl carbon is stable until
lone pair to the acid or water How it works: Oxidation of alcohols
aluminum is added to
quench. 7KHPHFKDQLVPIRUR[LGDWLRQRIDOFRKROVE\'HVV0DUWLQSHULRGLQDQHLVDOPRVW
QHYHUFRYHUHGLQLQWURGXFWRU\WH[WERRNV+RZHYHULWLVLQFOXGHGKHUHLQWKH
How it works: Conversion of nitriles to aldehydes LQWHUHVWVRIFRPSOHWHQHVV0HFKDQLVPLVWKHVDPHIRUSULPDU\DQGVHFRQGDU\
DOFRKROV
Deprotonation by acetate
ion gives acetic acid.
Imine
formation
*OUIFmSTUTUFQ XBUFS
Coordination of the Delivery of hydride to coordinates to DMP
nitrogen lone pair to the nitrile carbon Deprotonation
and displaces acetate
the aluminum
Dissociation of acetate
Aldehyde ion and deprotonation of
the C-H bond leads to
oxidation of the alcohol.
Hydrolysis gives
an aldehyde

Index Index
36 37
Fe FeBr3
Iron 0YVU000)YVTPKL
Also known as:)HUULFEURPLGHLURQWULEURPLGH

:KDWLW·VXVHGIRU,URQPHWDO )H ZLOOUHGXFHQLWURJURXSVWRDPLQHVLQWKHSUHV- :KDWLW·VXVHGIRU/HZLVDFLGSURPRWHUIRUHOHFWURSKLOLFDURPDWLFVXEVWLWXWLRQ
HQFHRIDVWURQJDFLGVXFKDV+&O Similar to:$O%U3$O&O3)H&O3
Similar to:7LQ 6Q ]LQF =Q
([DPSOH(OHFWURSKLOLFEURPLQDWLRQFRQYHUVLRQRIDUHQHVWRDU\OEURPLGHV
Example 1: Reduction: conversion of nitro groups to primary amines ([DPSOH)ULHGHO&UDIWVDF\ODWLRQFRQYHUVLRQRIDUHQHVWRDU\ONHWRQHV
How it works: Reduction of nitro groups ([DPSOH)ULHGHO&UDIWVDON\ODWLRQFRQYHUVLRQRIDUHQHVWRDON\ODUHQHV
7KHPHFKDQLVPIRUWKLVUHDFWLRQLVFRPSOH[DQGSURFHHGVLQPXOWLSOHVWHSV
,WOLNHO\SURFHHGVVLPLODUO\WRWKDWGUDZQLQWKHVHFWLRQIRUWLQ
How it works: Electrophilic bromination
)H%U3LVD/HZLVDFLGWKDWFDQFRRUGLQDWHWRKDORJHQV,QGRLQJVRLW
LQFUHDVHVWKHLUHOHFWURSKLOLFLW\PDNLQJWKHPPXFKPRUHUHDFWLYH
This is a more electrophilic source of bromine

than Br2
7ULYLD)H%U3FDQDOVREHXVHGIRUFKORULQDWLRQEXW)H&O3LVPRUHRIWHQXVHG
7KHUHDVRQLVWKDWVPDOODPRXQWVRIKDOLGHVFUDPEOLQJFDQRFFXUZKHQ)H%U3
LVXVHGZLWK&O

Index Index
38 39
FeBr3 -L*S3
JVU[PU\LK 0YVU000JOSVYPKL
How it works: Friedel-Crafts Acylation Also known as:)HUULFFKORULGHLURQWULFKORULGH

&RRUGLQDWLRQRIWKH/HZLVDFLG)H%U3WRWKH%URIWKHDFLGKDOLGHPDNHV%UD :KDWLW·VXVHGIRU,URQ ,,, FKORULGH IHUULFFKORULGH LVD/HZLVDFLG,WLVXVHIXO
EHWWHUOHDYLQJJURXSIDFLOLWDWLQJIRUPDWLRQRIWKHFDUERFDWLRQ ´DF\OLXPLRQµLQ LQSURPRWLQJWKHFKORULQDWLRQRIDURPDWLFFRPSRXQGVZLWK&ODVZHOODVLQWKH
WKLVFDVH )ULHGHO&UDIWVDON\ODWLRQDQGDF\ODWLRQUHDFWLRQV
Similar to:$O&O3$O%U3)H%U3
Acylium ion ([DPSOH(OHFWURSKLOLFFKORULQDWLRQFRQYHUVLRQRIDUHQHVWRDU\OFKORULGHV
1H[WDWWDFNRIWKHDURPDWLFULQJXSRQWKHFDUERFDWLRQIROORZHGE\GHSURWRQDWLRQ
JLYHVWKHDU\ONHWRQH
How it works:
$VLPLODUSURFHVVRSHUDWHVIRUWKH)ULHGHO&UDIWVDON\ODWLRQ QRWSLFWXUHG
6HHVHFWLRQVRQ$O&O3DQG)H%U3)H&O3ZRUNVLQH[DFWO\WKHVDPHZD\
Br
EF g

Index Index
40 41
Grignard Reagents Grignard reagents
JVU[PU\LK
Also known as:2UJDQRPDJQHVLXPUHDJHQWV Example 6: Reaction with epoxides
:KDWLW·VXVHGIRU([WUHPHO\JRRGQXFOHRSKLOHUHDFWVZLWKHOHFWURSKLOHVVXFKDV
FDUERQ\OFRPSRXQGV DOGHK\GHVNHWRQHVHVWHUVFDUERQGLR[LGHHWF DQGHSR[-
LGHV,QDGGLWLRQ*ULJQDUGUHDJHQWVDUHYHU\VWURQJEDVHVDQGZLOOUHDFWZLWKDFLGLF
K\GURJHQV
Similar to:2UJDQROLWKLXPUHDJHQWV 5²/L
Example 7: Reaction with carbon dioxide
Example 1: Conversion of alkyl or alkenyl halides to Grignard reagents 7KHSXUSVRHRIDFLGLQ

WKHVHFRQGVWHSLVWR
*ULJQDUGVFDQEHIRUPHGIURPDON\ORU SURWRQDWHWKHQHJDWLYHO\
DONHQ\OFKORULGHVEURPLGHVRULRGLGHV FKDUJHGR[\JHQ
QHYHUÁXRULGHV Example 8: Reaction with acidic hydrogens
Example 2: Conversion of aldehydes to secondary alcohols
$FLGLVDGGHGLQ 7KLVFDQEHXVHGWRLQWURGXFHGHXWHULXP
WKHVHFRQGVWHS 'HXWHULXPLVWKHKHDY\
WRSURWRQDWHWKH LVRWRSHRIK\GURJHQ
QHJDWLYHO\FKDUJHG
Example 3: Conversion of ketones to tertiary alcohols R[\JHQ How it works: Addition to aldehydes and ketones
*ULJQDUGUHDJHQWVDUHH[WUHPHO\VWURQJQXFOHRSKLOHV7KHHOHFWURQVLQWKH
&²0JERQGDUHKHDYLO\SRODUL]HGWRZDUGVFDUERQ
Example 4: Conversion of esters to tertiary alcohols

*ULJQDUG
UHDJHQWV 7KHUHIRUH*ULJQDUGUHDJHQWVZLOOUHDFWZHOOZLWKHOHFWURSKLOHVVXFKDV
DGGWZLFHWR DOGHK\GHVDQGNHWRQHV
HVWHUVDFLG
KDOLGHVDQG
Example 5: Conversion of acyl halides to tertiary alcohols DQK\GULGHV
$FLGLVDGGHGDIWHUFRPSOHWLRQRIWKHDGGLWLRQVWHS

Index Index
42 43
Grignard Reagents H2
JVU[PU\LK Hydrogen
How it works: Addition to epoxides :KDWLW·VXVHGIRU+\GURJHQJDVLVXVHGIRUWKHUHGXFWLRQRIDONHQHVDON\QHV

DQGPDQ\RWKHUVSHFLHVZLWKPXOWLSOHERQGVLQFRQFHUWZLWKFDWDO\VWVVXFKDV
3G&DQG3W
([DPSOH+\GURJHQDWLRQFRQYHUVLRQRIDONHQHVWRDONDQHV
How it works: Addition to esters

7KHVHSURFHHGWKURXJKDWZRVWHSPHFKDQLVPDGGLWLRQIROORZHGE\HOLPLQDWLRQ ([DPSOH+\GURJHQDWLRQFRQYHUVLRQRIDON\QHVWRDONDQHV
$FLGLVDGGHGDWWKHHQGWRREWDLQWKHDOFRKRO
([DPSOH/LQGODUUHGXFWLRQFRQYHUVLRQRIDON\QHVWRDONHQHV
Addition of Grignard Elimination of the OR group

reagent to the ester then forms the ketone ([DPSOH5HGXFWLRQFRQYHUVLRQRIQLWURJURXSVWRSULPDU\DPLQHV
A second equiv-
alent of Grignard
reagent then adds
to the ketone ([DPSOH+\GURJHQDWLRQFRQYHUVLRQRIQLWULOHVWRSULPDU\DPLQHV
Finally, acid [HX here]

is added to obtain the
neutral alcohol ([DPSOH+\GURJHQDWLRQFRQYHUVLRQRILPLQHVWRDPLQHV
7KHVDPHPHFKDQLVPRSHUDWHVIRUDFLGKDOLGHVDQGDQK\GULGHV ([DPSOH+\GURJHQDWLRQFRQYHUVLRQRIDUHQHVWRF\FORDONDQHV

Index Index
44 Acid Acid 45
+ +
H H3O
Anhydrous Acid Aqueous acid
Also known as:´SURWRQµ´SURWRQVRXUFHµ´DQK\GURXVDFLGµ Also known as:+\GURQLXPLRQ

:KDWLW·VXVHGIRU+LVDVKRUWKDQGWHUPIRU´DQK\GURXVDFLGµ7KHUHLVDFWXDOO\ :KDWLW·VXVHGIRU7RRJHQHUDODÚHDJHQWµWREHFRPSHKHQVLYHO\FRYHUHG
QRVXFKUHDJHQWDV´+µEHFDXVHSRVLWLYHFKDUJHQHYHUH[LVWVZLWKRXWDQHJDWLYH KHUH+32LVDJHQHULFWHUPIRU´DTXHRXVDFLGµRPLWWLQJWKHQHJDWLYHFRXQWHULRQ
FRXQWHULRQ7KHWHUP+LVDFRPPRQVKRUWKDQGUHIHUULQJWRDJHQHULFDFLGZKHUH ZKLFKJHQHUDOO\GRHVQRWSDUWLFLSDWHLQUHDFWLRQV %URDGO\VSHDNLQJDTXHRXV
WKHLGHQWLW\RIWKHQHJDWLYHO\FKDUJHG´VSHFWDWRULRQµLVQRWLPSRUWDQWDQGQRZDWHU DFLGLVXVHGIRUPDQ\K\GURO\VLVUHDFWLRQVDVZHOODVZKHQDUHDFWLRQUHTXLUHV
LVSUHVHQW
´DFLGZRUNXSµ
6LPLODUWR6XOIXULFDFLG +624 WRVLFDFLG 7V2+ DQGSKRVSKRULFDFLG+3324
DUHDOOHTXLYDOHQWWR´+µ6HHWKHVHVHFWLRQVIRUVSHFLÀFH[DPSOHV (TXLYDOHQWWR+2+624+2+3324
Aqueous acid protonates
7KHUHDUHWRRPDQ\XVHVRIDQK\GURXVDFLGWRKRSHWREHFRPSUHKHQVLYHKHUH the negatively charged alkoxide,
7KUHHLOOXVWUDWLYHH[DPSOHVDUHJLYHQ Example 1: Acidic workup giving the neutral alcohol
Example 1: Acid workup
0DQ\UHDFWLRQVIRUPDQLRQVSDUWLFXODUO\RQR[\JHQDQGDFLGZRUNXSVHUYHVWR
SURWRQDWHWKHDQLRQDQGGHOLYHUDQHXWUDOFRPSRXQG2IWHQVHHQDIWHUDGGLWLRQ
RI*ULJQDUGRUJDQROLWKLXPUHDJHQWVDQGUHGXFLQJDJHQWVWRFDUERQ\OV many similar examples of aqueous
workup throughout the Reagent Guide
Example 2: Hydration of alkenes to give alcohols
(TXLYDOHQWWR+32LQ
WKLVFDVH An equivalent reagent here
would be H2SO4/H2O
Example 2: To make neutral species into better leaving groups
&HUWDLQIXQFWLRQDOJURXSV DOFRKROVHWKHUVDPLQHV EHFRPHEHWWHUOHDYLQJJURXSV Example 3: Opening of epoxides to give trans diols
ZKHQSURWRQDWHGWRJLYHWKHLUFRQMXJDWHDFLG+ DVVKRUWKDQGIRU+6247V2+
RU+3324 FDQKHOSWRSURPRWHVXEVWLWXWLRQDQGHOLPLQDWLRQUHDFWLRQVWKDWIDLO Reaction proceeds through protonation
XQGHUQHXWUDOFRQGLWLRQV of oxygen followed by attack of water at
most substituted position
Example 4: Hydrolysis of esters to give carboxylic acids

([DPSOH7RPDNHFDUERQ\OVPRUHHOHFWURSKLOLF PRUHUHDFWLYHWRZDUGV
nucleophiles)
3URWRQDWLRQRIFDUERQ\OR[\JHQVPDNHVWKHDWWDFKHGFDUERQ\OFDUERQPRUH
UHDFWLYHWRZDUGVQXFOHRSKLOHV7KLVLVEHFDXVHWKHUHVRQDQFHIRUPZLWKDSRVLWLYH
FKDUJHRQFDUERQPDNHVDPRUHVLJQLÀFDQWFRQWULEXWLRQWRWKHK\EULGWKDQLQWKH Amides, nitriles, imines, and enamines can also be hydolyzed
XQSURWRQDWHGPROHFXOH by aqueous acid.
Example 5: Hydrolysis of acetals to give ketones
Protonation of a carbonyl
oxygen by H+ is a key step in
many reactions
4JHOJmDBOUSFTPOBODFGPSN
@bohring_bot
3 very reactive carbon!
Organic Chemistry Reagent Guide Index http://masterorganicchemistry.com Index

Index Index
46 47
HBr HBr
/`KYVIYVTPJHJPK
c JVU[PU\LK
:KDWLW·VXVHGIRU+\GUREURPLFDFLGLVDVWURQJDFLG,WFDQDGGWRFRPSRXQGV How it works: Addition to alkynes

ZLWKPXOWLSOHERQGVVXFKDVDONHQHVDQGDON\QHV,WFDQDOVRUHDFWZLWKSULPDU\ $GGLWLRQRIHTXLYDOHQWRI+%UZLOOOHDGWRDYLQ\OEURPLGHDGGLWLRQRIDVHFRQG
VHFRQGDU\DQGWHUWLDU\DOFRKROVWRIRUPDON\OEURPLGHV HTXLYDOHQWOHDGVWRWKHJHPLQDOGLEURPLGH
Attack of bromide
Similar to:+&O+, upon carbocation
([DPSOH+\GURKDORJHQDWLRQFRQYHUVLRQRIDONHQHVWRDON\OEURPLGHV
Note that the bromine adds to the Formation of most

most substituted carbon: stable carbocation
<Markovnikov= selectivity
Attack of bromide
([DPSOH+\GURKDORJHQDWLRQFRQYHUVLRQRIDON\QHVWRDONHQ\OEURPLGHV upon carbocation
Formation of most
stable carbocation
([DPSOH+\GURKDORJHQDWLRQFRQYHUVLRQRIDON\QHVWRJHPLQDOGLEURPLGHV How it works: Formation of alkyl bromides from alcohols
3URWRQDWLRQRI2+E\+%UPDNHVDJRRGOHDYLQJJURXS +2 :KHQDVWDEOHFDU-
ERFDWLRQFDQQRWEHIRUPHGWKHUHDFWLRQSURFHHGVYLDDQ6NSDWKZD\
backside
([DPSOH)UHHUDGLFDODGGLWLRQFRQYHUVLRQRIDONHQHVWRDON\OEURPLGHV protonation attack
Note here that the bromine

7HUWLDU\DOFRKROVWHQGWRSURFHHGWKURXJKDQ61SDWKZD\
adds to the least substituted
carbon: attack of bromide ion
<anti-Markovnikov= selectivity
protonation
([DPSOH&RQYHUVLRQRIDOFRKROVWRDON\OEURPLGHV 6N2)
Primary alcohol,
How it works: Free radical addition of HBr to alkenes
hence SN2 here.
3HUR[LGHV JHQHUDOIRUPXOD5225 KDYHDZHDN2²2ERQGDQGZLOOIUDJPHQW
KRPRO\WLFDOO\XSRQWUHDWPHQWZLWKKHDWRUOLJKWWRJLYHSHUR[\UDGLFDOV
([DPSOH&RQYHUVLRQRIDOFRKROVWRDON\OEURPLGHV 6N1)
heat or light
Tertiary alcohol,
hence SN1 3HUR[\UDGLFDOVDUHYHU\UHDFWLYHWKH\ZLOOUHDGLO\UHPRYHK\GURJHQIURPYDULRXV
JURXSV HJ+%U JLYLQJULVHWRIUHHUDGLFDOFKDLQSURFHVVHV
only a catalytic amount of perox-
How it works: Addition to alkenes Propagation step 1: ides are required to initiate the
Step 1: protonation of alkene to Step 2: attack of bromide ion on reaction
give most stable carbocation the carbocation Here, bromine radical adds to the alkene.
Propagation step 2: Note that addition occurs at the less sub-
stituted carbon; this gives rise to the most
stable free radical (secondary in this case)

Index Index
48 49
/*S /*S
/`KYVJOSVYPJHJPK JVU[PU\LK
:KDWLW·VXVHGIRU+\GURFKORULFDFLGLVDVWURQJDFLG$VDUHDJHQWLWFDQUHDFW How it works: Addition to alkynes

ZLWKPXOWLSOHERQGVLQDONHQHVDQGDON\QHVIRUPLQJFKORULQDWHGFRPSRXQGV,W
FDQDOVRFRQYHUWDOFRKROVWRDON\OFKORULGHV $GGLWLRQRIHTXLYDOHQWRI+%UZLOOOHDGWRDYLQ\OEURPLGHDGGLWLRQRIDVHFRQG
HTXLYDOHQWOHDGVWRWKHJHPLQDOGLEURPLGH
Similar to:+%U+,
Attack of chloride
([DPSOH+\GURKDORJHQDWLRQFRQYHUVLRQRIDONHQHVWRDON\OFKORULGHV
upon carbocation
Note that the chlorine adds to the
most substituted carbon:
<Markovnikov= selectivity
([DPSOH+\GURKDORJHQDWLRQFRQYHUVLRQRIDON\QHVWRDONHQ\OFKORULGHV Formation of most
stable carbocation
Attack of chloride
upon carbocation
([DPSOH+\GURKDORJHQDWLRQFRQYHUVLRQRIDON\QHVWRJHPLQDOGLFKORULGHV Formation of most
stable carbocation
How it works: Formation of alkyl chlorides from alcohols

3URWRQDWLRQRI2+E\+&OPDNHVDJRRGOHDYLQJJURXS +2 :KHQDVWDEOH
([DPSOH&RQYHUVLRQRIDOFRKROVWRDON\OFKORULGHV 6N2) FDUERFDWLRQFDQQRWEHIRUPHGWKHUHDFWLRQSURFHHGVYLDDQ6NSDWKZD\
Primary alcohol,
therefore SN2 backside attack
most likely of Cl
protonation
([DPSOH&RQYHUVLRQRIDOFRKROVWRDON\OFKORULGHV 6N1)
Reaction proceeds via backside
Tertiary alcohol, attack on the primary carbon
therefore SN1 here
,QVLWXDWLRQVZKHUHDPRUHVWDEOHFDUERFDWLRQFDQEHIRUPHG HJZLWKWHUWLDU\
How it works: Addition to alkenes DOFRKROV WKHUHDFWLRQSURFHHGVYLD6N
Step 1: protonation of
alkene to give the most
Step 2: attack of chloride ion on
stable carbocation attack of bromide ion
the carbocation
protonation
loss of
leaving
group

Index Index
50 51
H2CrO4 H2CrO4
Chromic acid JVU[PU\LK
How it works: Oxidation of aldehydes to carboxylic acids
Also known as:&KURPLFDFLGLVRIWHQIRUPHGLQVROXWLRQE\DGGLQJDFLGWRVDOWV

RIFKURPDWHRUGLFKURPDWH([DPSOHV
K&U27+321D&U27+321D&U24+32.&U24+32&U23+32
$OORIWKHVHFRQGLWLRQVDUHHTXLYDOHQWWR+&U246RLVWKH´-RQHV5HDJHQWµ
:KDWLW·VXVHGIRU&KURPLFDFLGLVDVWURQJR[LGL]LQJDJHQW,WZLOOR[LGL]H
VHFRQGDU\DOFRKROVWRNHWRQHVDQGSULPDU\DOFRKROVWRFDUER[\OLFDFLGV aldehyde
hydrate
Similar to: .0Q24
Example 1: Oxidation of secondary alcohols to give ketones
Example 2: Oxidation of primary alcohols to give carboxylic acids
The base here can be

water or the conjugate
base of the acid
How it works: Oxidation of alcohols
$TXHRXVDFLGLFFRQGLWLRQVFRQYHUWVRGLXPRUSRWDVVLXPGLFKURPDWHLQWR
FKURPLFDFLGZKLFKLVWKHDFWLYHR[LGDQWKHUH
Chromic acid
&KURPLFDFLGLVWKHQDWWDFNHGE\R[\JHQ'HSURWRQDWLRQRIWKH&+ERQG
UHVXOWVLQR[LGDWLRQRIWKHDOFRKRO
Water is basic
enough to
remove a proton
here

Index Index
52 53
/N6(J2 /N6(J2
Mercuric Acetate JVU[PU\LK
:KDWLW·VXVHGIRU0HUFXULFDFHWDWHLVDXVHIXOUHDJHQWIRUWKHR[\PHUFXUDWLRQ How it works: Oxymercuration of alkynes

RIDONHQHVDQGDON\QHV,WPDNHVGRXEOHERQGVPRUHUHDFWLYHWRZDUGVQXFOHRS- Treatment of an alkyne with Hg(OAc)2 and water leads to the formation of an
KLOLFDWWDFNE\QXFOHRSKLOHVVXFKDVZDWHUDQGDOFRKROV7KHPHUFXU\LVUHPRYHG enol, which converts to a ketone through tautomerization.
E\XVLQJ1D%+4 RU+624LQWKHFDVHRIDGGLWLRQWRDON\QHV
Similar to:+J62 +J 27)$ LVDUHODWHGUHDJHQW 7)$ WULÁXRURDFHWDWH
([DPSOH2[\PHUFXUDWLRQFRQYHUVLRQRIDONHQHVWRDOFRKROV
Attack of water at
the most substituted
carbon (Markovnikov
addition)
([DPSOH2[\PHUFXUDWLRQFRQYHUVLRQRIDONHQHVWRHWKHUV
Acid replaces the
Tautomerization mercury with H
([DPSOH2[\PHUFXUDWLRQFRQYHUVLRQRIDON\QHVWRNHWRQHV Tautomerization favors the

ketone
7ULYLDOGHWDLOVLQFHPHUFXU\LVOLEHUDWHGDV+JWKLVSURFHVVLVFDWDO\WLFLQ
How it works: Oxymercuration of alkenes PHUFXU\
,QWKHR[\PHUFXUDWLRQUHDFWLRQDQDONHQHUHDFWVZLWKPHUFXULFDFHWDWHWRJLYHD
PHPEHUHGULQJFRQWDLQLQJPHUFXU\ D´PHUFXULQLXPLRQµ 7KLVLVWKHQDWWDFNHG
E\DQXFOHRSKLOLFVROYHQW HJZDWHU DWWKHPRVWVXEVWLWXWHGFDUERQ
attack at most substituted carbon
(<Markovnikov= addition)
mercurinium ion
NaBH4 converts the C3Hg

bond to a C3H bond
The reduction goes through a free radical on carbon,

so there is no syn/anti selectivity
7KHUHVXOWRIWKHR[\PHUFXUDWLRQUHDFWLRQLVD0DUYNRYQLNRYDGGLWLRQRIZDWHU

WRDQDONHQH$IWHUWUHDWPHQWZLWK1D%+4VROLGPHUFXU\ LVREWDLQHG
Index Index
54 55
HgSO4 HI
4LYJ\YPJ:\SMH[L Hydroiodic acid
:KDWLW·VXVHGIRU0HUFXULFVXOIDWHLVD/HZLVDFLG,QWKHSUHVHQFHRIDTXHRXV :KDWLW·VXVHGIRU+\GURLRGLFDFLGLVDVWURQJDFLG$VDUHDJHQWLWFDQDGG
DFLG ´+32µRU+624+2 LWZLOOSHUIRUPWKHR[\PHUFXUDWLRQRIDON\QHVWRNHWRQHV K\GURJHQDQGLRGLQHDFURVVFRPSRXQGVZLWKPXOWLSOHERQGVVXFKDVDONHQHVDQG
DON\QHV,WLVDOVRXVHIXOIRUWKHFOHDYDJHRIHWKHUVDQGWKHFRQYHUVLRQRIDOFRKROV
Similar to:0HUFXULFDFHWDWH +J 2$F WRDON\OKDOLGHV

Similar to:+%U+&O
([DPSOH2[\PHUFXUDWLRQFRQYHUVLRQRIDON\QHVWRNHWRQHV
([DPSOH+\GURKDORJHQDWLRQFRQYHUVLRQRIDONHQHVWRDON\OLRGLGHV
Note that iodine adds to the most
substituted carbon (Markovnikov
selectivity)
([DPSOH+\GURKDORJHQDWLRQFRQYHUVLRQRIDON\QHVWRDONHQ\OLRGLGHV
How it works: Oxymercuration of alkynes

2[\PHUFXUDWLRQRIDON\QHVRFFXUVWKURXJKDWWDFNRIWKHDON\QH3,ERQGRQ+J ([DPSOH+\GURKDORJHQDWLRQGRXEOHDGGLWLRQRI+,WRDON\QHVWRJLYH
IROORZHGE\DWWDFNRIZDWHUSURWRQDWLRQGHPHUFXUDWLRQDQGWDXWRPHUL]DWLRQRIWKH geminal diiodides
UHVXOWLQJHQROWRJLYHWKHNHWRQH
Formation of mercurinium
ion
([DPSOH6XEVWLWXWLRQFRQYHUVLRQRIDOFRKROVWRDON\OLRGLGHV 6N2)
Deprotonation Primary alcohol

goes through
an SN2 process
Attack of H2O
([DPSOH6XEVWLWXWLRQFRQYHUVLRQRIDOFRKROVWRDON\OLRGLGHV 6N1)
Note - Markovnikov selective
Tertiary alcohol can form a
relatively stable carbocation,
therefore an SN1 process is
Enol favorable
Example 6: Conversion of ethers to alcohols and alkyl iodides
How it works: Addition to alkenes

Loss of mercury ,QWKHÀUVWVWHSWKHDONHQHLVSURWRQDWHGWRJLYHWKHPRUHVXEVWLWXWHGFDUERQ
Attack of enol on IROORZHGE\DWWDFNRIWKHLRGLGHLRQWRJLYHWKHDON\OLRGLGH
Tautomerization H2SO4
Step 1: protonation of
alkene to give the most Step 2: attack of iodide ion on the
stable carbocation carbocation

Index Index
56 57
HI HIO4
JVU[PU\LK Periodic acid
How it works: Addition to alkynes :KDWLW·VXVHGIRU3HULRGLFDFLGLVDVWURQJR[LGL]LQJDJHQW,WLVPRVWFRPPRQO\

$GGLWLRQRIHTXLYDOHQWRI+,ZLOOOHDGWRDQDONHQ\OLRGLGHDGGLWLRQRID XVHGIRUWKHR[LGDWLYHFOHDYDJHRIGLROV YLFLQDOGLROV WRJLYHDOGHK\GHVDQG
VHFRQGHTXLYDOHQWOHDGVWRWKHJHPLQDOGLLRGLGH NHWRQHV
Attack of iodide Similar to: 6RGLXPSHULRGDWH 1D,24 /HDG ,9 DFHWDWH>3E 2$F 4@

Alkenyl iodide
Example 1: Cleavage of diols to give aldehydes/ketones
(vinyl iodide)
Formation of most
stable carbocation VHFRQGHTXLYDOHQW
Formation of most
Attack of iodide stable carbocation
How it works: Conversion of alcohols to alkyl iodides

3URWRQDWLRQFRQYHUWV2+WRDEHWWHUOHDYLQJJURXS +2 6NGRPLQDQWIRUSULPDU\ How it works: Cleavage of diols to give aldehydes/ketones
3HULRGLFDFLGLVDVWURQJR[LGL]LQJDJHQW6LPLODUWR3E 2$F 4LWFDQFOHDYH

GLROV YLFLQDOGLROV WRJLYHWKHFRUUHVSRQGLQJDOGHK\GHVRUNHWRQHV
6NGRPLQDWHVZKHQDUHODWLYHO\VWDEOHFDUERFDWLRQFDQIRUP
Nucleophilic attack
Protonation
Carbocation formation
How it works: Cleavage of ethers
'HSHQGLQJRQWKHVWUXFWXUHRIWKHHWKHUFOHDYDJHFDQRFFXUHLWKHUWKURXJK
6NRU6N
Protonation Backside attack

Nucleophilic attack
Protonation
Notice how iodine starts in the
@bohring_bot
Carbocation formation (VII) oxidation state and goes to
(tertiary) (V) (it has been reduced)
2
Index Index
58 59
/656 /563
5P[YV\Z(JPK 5P[YPJ(JPK
Also known as:+12(TXLYDOHQWWR1D12+624RU1D12+&O :KDWLW·VXVHGIRU$VWURQJDFLG+123LVXVHGDVDUHDJHQWLQWKHDGGLWLRQRI

12WRDURPDWLFFRPSRXQGV ´QLWUDWLRQµ ,WZLOODOVRR[LGL]HSULPDU\DOFRKROVDQG
:KDWLW·VXVHGIRU1LWURXVDFLGLVSULPDULO\XVHGWRFRQYHUWDURPDWLFDPLQHVWR DOGHK\GHVWRFDUER[\OLFDFLGV
GLD]RQLXPVDOWVZKLFKFDQEHFRQYHUWHGLQWRPDQ\GLIIHUHQWFRPSRXQGVYLDWKH
6DQGPH\HUUHDFWLRQ,WFDQDOVREHPDGHIURP1D12LIDVWURQJDFLGVXFKDV ([DPSOH1LWUDWLRQFRQYHUVLRQRIDUHQHVWRQLWURDUHQHV
+624RU+&OLVDGGHG
H2SO4 is a catalyst in this
reaction
([DPSOH&RQYHUVLRQRIDURPDWLFDPLQHVWRGLD]RQLXPVDOWV
([DPSOH2[LGDWLRQFRQYHUVLRQRIDOGHK\GHVSULPDU\DOFRKROVWR
carboxylic acids
Diazonium salt This reaction is often introduced

Note: other acids beside HCl can be used in the context of carbohydrate
as the acid here (such as H2SO4) chemistry. Note how the top and
botttom carbons have both been
How it works: Formation of diazonium salts oxidized.
1LWURXVDFLGUHDFWVZLWKDURPDWLFDPLQHVWRIRUPGLD]RQLXPVDOWV7KHUHDF-
WLRQLVJUHDWO\DVVLVWHGE\VWURQJDFLGVVXFKDV+&ORU+624
How it works: Nitration of aromatics
Acid activates the N=O bond ,QWKHSUHVHQFHRIDVWURQJDFLGVXFKDV+624+123LVSURWRQDWHGDQGORVHV
toward attack by the amine ZDWHUWRIRUPWKHQLWURQLXPLRQ 12 DYHU\UHDFWLYHHOHFWURSKLOH
Loss of water
proton Protonation
transfer Nitronium ion
7KH12 LVWKHQDWWDFNHGE\WKHDURPDWLFULQJWRJLYHDFDUERFDWLRQZKLFKLV

WKHQGHSURWRQDWHGWRUHVWRUHDURPDWLFLW\+624LVUHJHQHUDWHGZKLFKFDQWKHQ
JRRQWRUHDFWZLWKDQRWKHUHTXLYDOHQWRI+123 LWLVDFDWDO\VWKHUH
Step 1:
Electrophilic addition
proton
transfer Step 2: Deprotonation
+624
+ H2O Note that acid is regenerated
Diazonium salt
@bohring_bot
here; it acts as a catalyst in
this reaction.
f
Index Index
60 61
H2O2 H2O2
Hydrogen peroxide JVU[PU\LK
:KDWLW·VXVHGIRU+\GURJHQSHUR[LGHLVXVHGDVDQR[LGDQWLQWKHK\GURERUDWLRQ How it works: Oxidative workup for ozonolysis

RIDONHQHVDQGDON\QHVFRQYHUWLQJWKH&²%ERQGLQWRD&²2ERQG,WLVDOVRXVHG
LQWKHR[LGDWLYHZRUNXSRIR]RQRO\VLVFRQYHUWLQJDOGHK\GHVLQWRFDUER[\OLFDFLGV +\GURJHQSHUR[LGHFDQR[LGL]HDOGHK\GHVWRFDUER[\OLFDFLGV7KLVLVLWKH
EDVLVIRU´R[LGDWLYHZRUNXSµRIWKHR]RQRO\VLVUHDFWLRQZKHUHWKHDOGHK\GH
LVWUHDWHGZLWKDTXHRXV+2 PLQRUQRWHDGGLWLRQRIDEDVHVXFKDV1D2+
Example 1: As an oxidant in the hydroboration reaction
VSHHGVXSWKLVUHDFWLRQ
([DPSOH)RUR[LGDWLYHZRUNXSLQR]RQRO\VLV
Note that carbox-
ylic acids (not
aldehydes) are the Ozonide Addition of H2O2
products here (breaks open upon to aldehyde
heating)
How it works: Hydroboration of alkenes
+\GURJHQSHUR[LGHLVXVHGLQFRQFHUWZLWKWKHVWURQJEDVH1D2+'HSURWRQDWLRQ
RI+2JLYHVLWVFRQMXJDWHEDVHZKLFKLVDPRUHUHDFWLYHQXFOHRSKLOH
Proton transfer
7KHSHUR[LGHLRQWKHQDWWDFNVERURQ,QWKHNH\VWHSDUHDUUDQJHPHQWRFFXUV Deprotonation
EUHDNLQJWKHZHDN N-PRO 2²2ERQG
/PUFUIFmOBMEFQSPUPOBUJPO
step is the rate-limiting step; it
Attack of peroxide Rearrangement is greatly accelerated by addi-
tion of base.
Carboxylic acid
7KH%²2ERQGLVWKHQEURNHQWKURXJKIXUWKHUDWWDFN Hydrolysis
RI1D2+XSRQERURQ7KHQHJDWLYHO\FKDUJHGR[\JHQ
´DONR[LGHµ LVHYHQWXDOO\SURWRQDWHGE\ZDWHU

Index Index
62 63
H3PO4 H2SO4
Phosphoric acid :\SM\YPJHJPK
:KDWLW·VXVHGIRU3KRVSKRULFDFLGLVDPRGHUDWHO\VWURQJDFLG7KHFRQMXJDWH :KDWLW·VXVHGIRU6XOIXULFDFLGNQRZQWRDOFKHPLVWVDV´RLORIYLWULROµLVDVWURQJ
DFLGRI+3324LVDSRRUQXFOHRSKLOHVRSKRVSKRULFDFLGLVDQH[FHOOHQWDFLGWRXVH DFLG S.D² ,WLVSDUWLFXODUO\XVHIXOIRUHOLPLQDWLRQUHDFWLRQVVLQFHLWVFRQMXJDWH
IRUHOLPLQDWLRQUHDFWRQV EDVH>+624²@LVDYHU\SRRUQXFOHRSKLOH,WÀQGVXVHLQPDQ\RWKHUUHDFWLRQVDVD
Similar to:6XOIXULFDFLG +624 WRVLFDFLG 7V2+ JHQHUDOVWURQJDFLG
Similar to:pWROXHQHVXOIRQLFDFLG 7V2+

Example 1: Elimination of alcohols to give alkenes
Example 1: Elimination Ð conversion of alcohols to alkenes
How it works: Elimination of alcohols to give alkenes How it works: Elimination of alcohols
3URWRQDWLRQRIWKHDOFRKROE\SKRVSKRULFDFLGPDNHV2+LQWRDJRRG 3URWRQDWLRQRIWKHDOFRKROIRUPVLWVFRQMXJDWHDFLG>DQ´R[RQLXPLRQµ@ZKLFKKDV
OHDYLQJJURXS +2 ZKLFKGHSDUWVWRJLYHDFDUERFDWLRQ'HSURWRQDWLRQ DPXFKEHWWHUOHDYLQJJURXS +2 WKDQWKHDOFRKRO +2² /RVVRIZDWHUUHVXOWV
RIWKHFDUERQDGMDFHQWWRWKHFDUERFDWLRQOHDGVWRDQDONHQH WKLVLVDQ LQWKHIRUPDWLRQRIDFDUERFDWLRQ7KHUHVRQDQFHVWDELOL]HG+624DQLRQLVDSRRU
(PHFKDQLVP QXFOHRSKLOHDQGWHQGVQRWWRDGGWRWKHFDUERFDWLRQ XQOLNH+%UDQG+&OIRUH[DP-
SOH 'HSURWRQDWLRQHLWKHUE\+624²RUE\ZDWHUOHDGVWRIRUPDWLRQRIWKHDONHQH
DQGUHJHQHUDWLRQRIDFLG
Protonation Loss of H2O
Carbocation
Deprotonation to Protonation formation
give alkene
Deprotonation
Note resonance stability of

the HSO43 anion
H2SO4 is regenerated
(i.e. it is a catalyst)
$VZLWKPDQ\UHDFWLRQVWKDWSDVVWKURXJKFDUERFDWLRQVUHDUUDQJHPHQWVFDQ
RFFXULQVLWXDWLRQVZKHUHDPRUHVWDEOHFDUERFDWLRQFDQIRUPWKURXJKDK\GULGH
RUDON\OVKLIW

Index Index
64 65
I2 Iodine
Iodine JVU[PU\LK
:KDWLW·VXVHGIRU,RGLQHLVDQH[FHOOHQWHOHFWURSKLOHGXHWRWKHZHDN,²,ERQG How it works: Iodination of ketones

DSSUR[N-PRO>NFDOPRO@ ,WUHDFWVZLWKFDUERQFDUERQPXOWLSOHERQGV 7UHDWPHQWRINHWRQHVZLWKDFLG>´+;µ@FDWDO\]HVNHWRHQROWDXWRPHUL]DWLRQ$WWDFNRI
VXFKDVDONHQHVDQGDON\QHVDORQJZLWKRWKHUQXFOHRSKLOHV,WLVDOVRXVHGLQWKH LRGLQHE\WKHHQROWDXWRPHUIROORZHGE\GHSURWRQDWLRQJLYHVWKHLRGLQDWHGNHWRQH
LRGRIRUPUHDFWLRQ
Similar to:NLRGRVXFFLQLPLGH 1,6 SHUIRUPVPDQ\RIWKHVDPHUHDFWLRQV
([DPSOH,RGLQDWLRQFRQYHUVLRQRIDONHQHVWRYLFLQDOGLLRGLGHV
tautomerization
How it works: The haloform reaction

Example 2: Conversion of alkenes to iodohydrins 0HWK\ONHWRQHVWUHDWHGZLWKVWURQJEDVH HJ1D2+ IRUPHQRODWHVZKLFKDWWDFN
LRGLQH$IWHUFRPSOHWHUHSODFHPHQWRI+E\,WKH²&,3LRQFDQWKHQEHGLVSODFHG
IURPWKHNHWRQHJLYLQJDFDUER[\OLFDFLG
Example 3: Conversion of ketones to _LRGRNHWRQHV
H+ here refers to any

generic strong acid
Enolate formation Iodination
([DPSOH,RGRIRUPUHDFWLRQFRQYHUVLRQRIPHWK\ONHWRQHVWRFDUER[\OLF Enolate
acids formation
Iodination
How it works: Iodination of alkenes

7UHDWPHQWRIDQDONHQHZLWK,OHDGVWRIRUPDWLRQRIDQLRGRQLXPLRQZKLFKXQGHU-
JRHVEDFNVLGHDWWDFNE\LRGLGHLRQWRJLYHWKHWUDQVSURGXFW
Attack of The enantiomer Enolate Iodination
alkene upon Nucleophilic will also be formation
iodine attack formed in this
example.
Iodonium ion Na+
:KHQDQXFOHRSKLOLFVROYHQWVXFKDV+2RUDQDOFRKROLVSUHVHQWKDORK\GULQV
FDQIRUP +&,3
A halohydrin
Elimination of the 3CI3 Extra detail: under the
Addition of 3OH ion (a weak base) basic reaction condi-
tions, the carboxylic acid
@bohring_bot
will be deprotonated.
Acidic workup required.
2
66
KMnO4
Potassium permanganate
Index
To
Index
KMnO4
JVU[PU\LK
67
:KDWLW·VXVHGIRU7KLVVWURQJR[LGL]LQJDJHQWZLOOR[LGL]HSULPDU\DOFRKROV DQG How it works: Oxidation of primary and secondary alcohols

DOGHK\GHV WRFDUER[\OLFDFLGVVHFRQGDU\DOFRKROVWRNHWRQHVIRUPGLROVIURP 3ULPDU\DOFRKROVDUHR[LGL]HGWRFDUER[\OLFDFLGVVHFRQGDU\DOFRKROVDUH
DONHQHVDQGR[LGDWLYHO\FOHDYHFDUERQFDUERQERQGV,WZLOODOVRR[LGL]H&+ R[LGL]HGWRNHWRQHV
ERQGVDGMDFHQWWRDURPDWLFULQJV
Similar to: K&U272V2423

([DPSOH2[LGDWLRQFRQYHUVLRQRISULPDU\DOFRKROVWRFDUER[\OLFDFLGV
Note: this is a potentially reasonable mechanism,
but the actual mechanism is complex and can Proton transfer
go down different pathways (some involving free
radicals, and some not fully understood!) Take
([DPSOH2[LGDWLRQFRQYHUVLRQRIVHFRQGDU\DOFRKROVWRNHWRQHV this with a grain of salt.
([DPSOH2[LGDWLRQFRQYHUVLRQRIDOGHK\GHVWRFDUER[\OLFDFLGV
$OGHK\GHVDUHQRWVWDEOHXQGHUWKHVHUHDFWLRQFRQGLWLRQVDQGZLOOEHIXUWKHU
R[LGL]HGWRFDUER[\OLFDFLGV
([DPSOH2[LGDWLYHFOHDYDJHFRQYHUVLRQRIDONHQHVWRNHWRQHVFDUER[
ylic acids
Aldehyde hydrate
Again, a suggested mechanism here, but KMnO4

oxidation can occur via multiple pathways (beyond
the scope of our discussion).
([DPSOH'LK\GUR[\ODWLRQFRQYHUVLRQRIDONHQHVWRYLFLQDOGLROV
Note that the stereochemistry

of the diol is <syn= How it works: Oxidation of aromatic side chains
7KHPHFKDQLVPIRUVLGHFKDLQR[LGDWLRQLVFRPSOH[ LQYROYHVIUHHUDGLFDOV DQGQRW
([DPSOH2[LGDWLRQFRQYHUVLRQRIDON\ODURPDWLFVWRFDUER[\OLFDFLGV FRPSOHWHO\XQGHUVWRRG,WUHTXLUHVWKDWWKHFDUERQDGMDFHQWWRWKHDUHQHKDYHDW
OHDVWRQH&²+ERQG
Note: only carbons adjacent
Note that this carbon
to the ring with at least one
lacks a C3H bond; it
C3H bond will be oxidized.
is not oxidized

Index Index
68 69
KMnO4 KOt-Bu
JVU[PU\LK Potassium tI\[V_PKL
How it works: Dihydroxylation of alkenes Also known as:.2& &+3 3SRWDVVLXPWHUWEXWR[LGH

8QGHUFROGGLOXWHEDVLFFRQGLWLRQV.0Q24ZLOOFRQYHUWDONHQHVLQWRGLROV
:KDWLW·VXVHGIRU3RWDVVLXPtEXWR[LGHLVDVWURQJVWHULFDOO\KLQGHUHGEDVH
YLFLQDOGLROV <LHOGVIRUWKLVSURFHVVDUHW\SLFDOO\ORZHUWKDQIRU2V24
7KHSURWRW\SLFDOÉXON\EDVHµLWLVXVHIXOLQHOLPLQDWLRQUHDFWLRQVIRUIRUPLQJWKH
OHVVVXEVWLWXWHG´QRQ=DLWVHYµ>VRPHWLPHVFDOOHG´+RIPDQQµ@DONHQHSURGXFW
Similar to:(VVHQWLDOO\LGHQWLFDOWR1D2W%XDQG/L2W%X>WKHVHDUHDOOWUHDWHGDVWKH
VDPHKHUH@/LWKLXPGLLVRSURS\ODPLGH /'$ LVDVWURQJHUEXON\EDVH
([DPSOH(OLPLQDWLRQFRQYHUVLRQRIDON\OKDOLGHVWRDONHQHV ´QRQ=DLWVHYµ
or ÒHofmannÓ alkene products)
In the absence of base, diols undergo Base (KOH) cleaves the

oxidative cleavage (see below) cyclic Mn compound
(<manganate ester=).
Hofmann product Zaitsev product
(major) (minor)
proton
transfer .%U+2& &+3 3
How it works: Formation of Ònon-ZaitsevÓ elimination products

(OLPLQDWLRQUHDFWLRQVJHQHUDOO\IDYRUIRUPDWLRQRIWKHPRUHVXEVWLWXWHGDONHQH
´=DLWVHY·VUXOHµ +RZHYHUVWHULFFODVKEHWZHHQWKHEXON\EDVHDQGDON\OJURXSV
FDQGLVIDYRUWKLVSDWKZD\
Acid workup leads to
the diol
How it works: Oxidative cleavage of alkenes

8QGHUDFLGLFFRQGLWLRQVYLFLQDOGLROVXQGHUJRR[LGDWLYHFOHDYDJH Steric clash
KMnO4 is protonated to give HMnO4 and adds to the alkene as above: Ònon-ZaitsevÓ or ÒZaitsevÓpathway
ÒHofmannÓ pathway
Disfavored
Favored
Oxidative
cleavage
Addition
<cyclic manganate
Oxidation to carboxylic
ester=
acid (as above)
7KHOHVVVXEVWLWXWHGDONHQH 7KHPRUHVXEVWLWXWHGDONHQH
´QRQ=DLWVHYSURGXFWµ LVWKH ´=DLWVHYSURGXFWµ LVWKHPLQRU
PDMRUSURGXFWKHUH SURGXFWKHUH

Index Index
70 71
KPhth LDA
7V[HZZP\T7O[OHSPTPKL 3P[OP\TKPPZVWYVW`SHTPKL
Also known as:SKWKDOLPLGHLRQ :KDWLW·VXVHGIRU/'$LVDVWURQJEXON\QRQQXFOHRSKLOLFEDVH,WLVWKHUHDJHQW

RIFKRLFHIRUVHOHFWLYHO\UHPRYLQJDSURWRQIURPWKHOHDVWKLQGHUHGFDUERQQH[WWRD
:KDWLW·VXVHGIRU6RGLXP RUSRWDVVLXP SKWKDOLPLGHLVDQLWURJHQFRQWDLQLQJ NHWRQH,WFDQDOVREHXVHGWRIRUPWKH´+RIPDQQµSURGXFWLQHOLPLQDWLRQUHDFWLRQV
QXFOHRSKLOHXVHGLQWKH*DELUHOV\QWKHVLV3RWDVVLXPSKWKDOLPLGHUHDFWVZLWK
Similar to:1D1+ LQVWUHQJWK .2W%X LQVL]H
DON\OKDOLGHVWRIRUPD&²1ERQGZKLFKLVWKHQFOHDYHGE\WUHDWPHQWZLWKK\GUD-
]LQHWRJLYHDSULPDU\DPLQH
Example 1: Conversion of ketones to enolates
([DPSOH6XEVWLWXWLRQIRUPDWLRQRIDON\OSKWKDOLPLGHVIURPDON\OKDOLGHV
Note that deprotonation Diisopropyl amine

occurs at the least sub-
stituted carbon
([DPSOH&RQYHUVLRQRISKWKDOLPLGHVWRSULPDU\DPLQHV DIWHUFOHDYDJH
with NH2NH2) Example 2: Eiimination of alkyl halides to give ÒHofmannÓ alkenes
<Hofmann= alkene product <Zaitsev= product

(major) (minor)
How it works: Substitution reaction How it works: Formation of less substituted enolates (ÒkineticÓ enolates)
,QWKHUHDFWLRQEHORZDVWURQJEDVH 1D+ LVXVHGWRGHSURWRQDWHSKWKDODPLGH 7KHEXON\LVRSURS\OJURXSVRI/'$PDNHLWDKLJKO\VHOHFWLYHEDVHIRUUHPRYLQJD

WRJLYHWKHFRQMXJDWHEDVHZKLFKWKHQSHUIRUPVDQ6NUHDFWLRQRQDSULPDU\ SURWRQIURPWKHOHVVKLQGHUHG_FDUERQRIWKHNHWRQH
DON\OKDOLGH
Tetrahydrofuran (THF) is a
common solvent for this reaction.
Low temperature maximizes
selectivity.
(Resonance forms of the Diisopropylamine (the con-

enolate) jugate acid of LDA)

Index Index
72 73
Li Li
Lithium
a JVU[PU\LK
How it works: Birch reduction
:KDWLW·VXVHGIRU/LWKLXPLVDUHGXFLQJDJHQW,WZLOOFRQYHUWDON\OKDOLGHVWRDON\O 7KH%LUFKUHGXFWLRQLVDXVHIXOZD\RIREWDLQLQJGLHQHVIURPDURPDWLFJURXSV$P-
OLWKLXPFRPSRXQGV,WLVVLPLODUWR DOWKRXJKDZHDNHUUHGXFLQJDJHQWWKDQ VRGLXP PRQLD 1+3 LVWKHXVXDOVROYHQWZLWKVPDOODPRXQWVRIDQDOFRKROVXFKDVt-%X2+
DQGSRWDVVLXP,WZLOODOVRIRUP+ZKHQWUHDWHGZLWKDOFRKROVJLYLQJOLWKLXPDONR[- SURYLGLQJDVRXUFHRISURWRQV
LGHV
Similar to:6RGLXP 1D 3RWDVVLXP .
Example 1: Conversion of alkyl halides to alkyllithiums
when an electron donating group

such as OMe is present, protonation
occurs on the meta position
Example 2: Conversion of alcohols to alkoxides
([DPSOH%LUFKUHGXFWLRQFRQYHUVLRQRIDUHQHVWRGLHQHV
Although t-BuOH is the most common

How it works: Formation of organolithium reagents alcohol used, MeOH, EtOH or i-PrOH
are all effective.
/LNHDOODONDOLPHWDOVOLWKLXPUHDGLO\JLYHVXSLWVVLQJOHYDOHQFHHOHFWURQ:KHQ
WUHDWHGZLWKDQDON\OKDOLGHLWZLOOIRUPDQDON\OOLWKLXPVSHFLHV7ZRHTXLYDOHQWVRI :KHQHOHFWURQZLWKGUDZLQJVXEVWLWXHQWVDUHSUHVHQWSURWRQDWLRQRFFXUVRQWKH
OLWKLXPDUHUHTXLUHGIRUWKLVUHDFWLRQ FDUERQDGMDFHQWWRWKHHOHFWURQZLWKGUDZLQJJURXS
This is called a <radical

anion= Note that protonation
occurs adjacent to
the electron with-
drawing group
Alkyllithiums: strong bases and

excellent nucleophiles.

Index Index
74 75
3PUKSHY»Z*H[HS`Z[ 3P(S/4
3P[OP\THS\TPU\TO`KYPKL
Also known as:3RLVRQHGFDWDO\VW3G&D&23 Also known as:/$+
:KDWLW·VXVHGIRU/LQGODU·VFDWDO\VWLVDSRLVRQHGSDOODGLXPPHWDOFDWDO\VWWKDW :KDWLW·VXVHGIRU/LWKLXPDOXPLQXPK\GULGHLVDYHU\VWURQJUHGXFLQJDJHQW,W
SHUIRUPVSDUWLDOK\GURJHQDWLRQVRIDON\QHVLQWKHSUHVHQFHRIK\GURJHQJDV + ,W ZLOOUHGXFHDOGHK\GHVNHWRQHVHVWHUVDQGFDUER[\OLFDFLGVWRDOFRKROVDPLGHV
DOZD\VJLYHVWKHcisDONHQHLQFRQWUDVWWR1D1+3ZKLFKJLYHVtrans DQGQLWULOHVWRDPLQHVDQGRSHQHSR[LGHVWRJLYHDOFRKROV
Similar to: 1LFNHOERULGH 1L% SDOODGLXPRQEDULXPVXOIDWH3G&D&23TXLQROLQH Similar to:1D%+4',%$//L$O+ 2W%X 3
([DPSOH5HGXFWLRQFRQYHUVLRQRIHVWHUVWRSULPDU\DOFRKROV
([DPSOH/LQGODUUHGXFWLRQFRQYHUVLRQRIDON\QHVWRDONHQHV
([DPSOH5HGXFWLRQFRQYHUVLRQRIFDUER[\OLFDFLGVWRSULPDU\DOFRKROV
([DPSOH5HGXFWLRQFRQYHUVLRQRIDPLGHVWRSULPDU\DPLQHV
How it works: Partial hydrogenation
2WKHUWKDQLWVORZHUDFWLYLW\ZKHQFRPSDUHGZLWKQRQSRLVRQHGPHWDOFDWDO\VWV
/LQGODU·VFDWDO\VWEHKDYHVLQDOOZD\VVLPLODUWRRWKHUKHWHURJHQHRXVPHWDOFDWD-
O\VWVVXFKDV3G&3W1LHWF VHHWKHVHVHSHUDWHO\ 7KHDON\QHDQGK\GURJHQ
DUHDGVRUEHGRQWRWKHPHWDOVXUIDFHDQGGHOLYHUHGLQcisIDVKLRQ ([DPSOH5HGXFWLRQFRQYHUVLRQRINHWRQHVWRVHFRQGDU\DOFRKROV
6RPHWLPHVWKHDURPDWLFDPLQHTXLQROLQHLVXVHGZKLFKDVVLVWVWKHVHOHFWLYLW\RI
WKHUHDFWLRQDQGSUHYHQWVWKHIRUPDWLRQRIDONDQHV
,WLVWKRXJKWWKDWWKHUROHRI3E OHDG LVWRUHGXFHWKHDPRXQWRI

+DGVRUEHGZKLOHTXLQROLQHKHOSVWRSUHYHQWWKHIRUPDWLRQRI ([DPSOH5HGXFWLRQFRQYHUVLRQRIQLWULOHVWRSULPDU\DPLQHV
XQZDQWHGE\SURGXFWV
Quinoline
([DPSOH5HGXFWLRQFRQYHUVLRQRID]LGHVWRSULPDU\DPLQHV
([DPSOH5HGXFWLRQFRQYHUVLRQRIHSR[LGHVWRDOFRKROV ULQJRSHQLQJ

Index Index
76 77
3P(S/4 3P(S/6t-)\3
JVU[PU\LK 3P[OP\T[YP[LY[I\[V_`
HS\TPU\TO`KYPKL
How it works: Reduction of esters, amides, and nitriles Also known as:/L$O+>2& &+3 3@
/LWKLXPDOXPLQXPK\GULGHLVDYHU\VWURQJUHGXFLQJDJHQWFDSDEOHRIUHDFWLQJ
ZLWKDZLGHYDULHW\RIIXQFWLRQDOJURXSV,WLVJHQHUDOO\QRWSRVVLEOHWRFRQWURO
UHDFWLRQVRI/L$O+4VRWKDWWKH\´VWRSµSDUWRIWKHZD\UHDFWLRQVRIHVWHUVJR :KDWLW·VXVHGIRU6WURQJEXON\UHGXFLQJDJHQW/HVVUHDFWLYHWKDQ/L$O+4LWZLOO
VWUDLJKWWRDOFRKROVIRULQVWDQFH FRQYHUWDF\OKDOLGHVWRDOGHK\GHV
Reduction of esters: Similar to:1D%+4',%$//L$O+4
Example 1: Reduction of acyl halides to aldehydes
Acyl bromides will

react similarly
The reaction does not stop at the
aldehyde stage, going straight
through to the alcohol
How it works: Reduction of acyl chlorides
7KHPHFKDQLVPIRUWKLVUHDFWLRQLVVLPLODUWR/L$O+46RORQJDVRQO\
RQHHTXLYDOHQWLVXVHGWKHDOGHK\GHZLOOQRWEHUHGXFHGIXUWKHUWRWKH
DOFRKRO
Reduction of amides:
Iminium
Here, oxygen is a better leaving ion
group than nitrogen!
Reduction of nitriles:

Index Index
78 79
m-CPBA m-CPBA
m-JOSVYVWLYV_ÌLUaVPJ JVU[PU\LK
acid
:KDWLW·VXVHGIRUP&3%$ VRPHWLPHVZULWWHQ0&3%$ LVDQR[LGL]LQJDJHQW How it works: Baeyer-Villiger reaction
,WVHHVXVHLQWZRPDLQZD\V)LUVWLWLVXVHGWRWUDQVIRUPDONHQHVLQWRHSR[LGHV
6HFRQGO\LWZLOOUHDFWZLWKNHWRQHVWRIRUPHVWHUVLQWKH%DH\HU9LOOLJHUUHDFWLRQ ,QWKH%DH\HU9LOOLJHUUHDFWLRQP&3%$DGGVWRDNHWRQHWRIRUPDWHWUDKHGUDO
LQWHUPHGLDWH,QWKHNH\VWHSWKHFDUERQPLJUDWHVWRR[\JHQEUHDNLQJWKHZHDN
Similar to: 3HUR[\DFHWLFDFLG>&+3&23+@WULÁXRURSHUR[\DFHWLFDFLG>&)3&23+@ 2²2ERQGDQGOHDGLQJWRWKHIRUPDWLRQRIDQHVWHU
DQGDQ\JHQHULFSHUR[\DFLG>5&23+RU5&222+@
([DPSOH(SR[LGDWLRQFRQYHUVLRQRIDONHQHVWRHSR[LGHV
Addition
Proton
transfer
([DPSOH%DH\HU9LOOLJHUUHDFWLRQFRQYHUVLRQRINHWRQHVWRHVWHUV
Migration
(key step!)
How it works: Epoxidation of alkenes

Proton
7UHDWPHQWRIDONHQHVZLWKP&3%$OHDGVWRWKHIRUPDWLRQRIHSR[LGHVWKURXJK transfer
Minor note: the rate of the addition reaction
DFRQFHUWHGWUDQVLWLRQVWDWH7KHUHDFWLRQLVFRPSOHWHO\VWHUHRVSHFLÀFWUDQV is increased by adding base, which depro-
DONHQHVDQGFLVDONHQHVJLYHVWHUHRLVRPHULFSURGXFWV tonates the peroxyacid, making it a better
nucleophile.
m-chloro benzoic acid

(byproduct)

Index Index
80 81
Mg 4Z*S
Magnesium
e 4L[OHULZ\SMVU`SJOSVYPKL
Also known as:0J0J V Also known as:0HV\OFKORULGH

:KDWLW·VXVHGIRU0DJQHVLXPPHWDOLVXVHGIRUWKHIRUPDWLRQRI*ULJQDUG :KDWLW·VXVHGIRU0HWKDQHVXOIRQ\OFKORULGHFRQYHUWVDOFRKROVLQWRJRRGOHDYLQJ
UHDJHQWVIURPDON\ODQGDONHQ\OKDOLGHV$FRPPRQVROYHQWIRUWKHVHUHDFWLRQV JURXSV,WEHKDYHVHVVHQWLDOO\LGHQWLFDOO\WR7V&OIRUWKLVSXUSRVH
DUHHWKHUVVXFKDVGLHWK\OHWKHU (W2
Similar to:SWROXHQHVXOIRQ\OFKORULGH 7V&O
Similar to: /LWKLXP LQWKHIRUPDWLRQRIDON\OOLWKLXPUHDJHQWV 1D.
Example 1: Conversion of alcohols to alkyl mesylates
Example 1: Conversion of alkyl halides to Grignard reagents
It is common to use a
Diethyl ether is a common weak base (pyridine in
solvent for this reaction this example) to react
with the HCl that is
Example 2: Conversion of alkenyl halides to Grignard reagents formed as a byproduct
of this reaction. This
helps the reaction pro-
ceed to completion.
How it works: Formation of Grignard reagents 7KHUHVXOWLQJDON\OVXOIRQDWHV ´PHV\ODWHVµ DUHH[FHOOHQWOHDYLQJJURXSVLQ

$OWKRXJKWKHPHFKDQLVPIRU*ULJQDUGIRUPDWLRQLVJHQHUDOO\QRWJLYHQLQWH[W- VXEVWLWXWLRQDQGHOLPLQDWLRQUHDFWLRQV)RUPHFKDQLVPVDQGH[DPSOHVVHH
ERRNVIRUPDWLRQRI*ULJQDUGUHDJHQWVJRHVWKURXJKDUDGLFDOSURFHVV WKHVHFWLRQRQ7V&O
Here, magnesium donates a single electron to Br, which forms a radical an-
ion. Homolytic fragmentation of the C3Br bond leads to a free radical, which
recombines with MgBr to give the Grignard reagent.

Index Index
82 83
5H53 5H
:VKP\THaPKL Sodium
:KDWLW·VXVHGIRU6RGLXPD]LGHLVDJRRGQXFOHRSKLOHWKDWUHDGLO\SDUWLFLSDWHVLQ :KDWLW·VXVHGIRU6RGLXPLVDYHU\VWURQJUHGXFLQJDJHQW,WZLOOUHGXFH
6NUHDFWLRQV$OWHUQDWLYHO\WKHVRGLXPRUOLWKLXPVDOWRID]LGHLRQFDQEHXVHGEXW DON\QHVWRDONHQHV WUDQVDON\QHVVSHFLÀFDOO\ ,WZLOOIRUPK\GURJHQJDVZKHQ
VRGLXPLVWKHPRVWFRPPRQ DGGHGWRDOFRKROVUHVXOWLQJLQDONR[LGHV,WZLOODOVRUHGXFHDURPDWLFJURXSVWR
Similar to:/L13.13 DONHQHV WKH%LUFKUHGXFWLRQ
([DPSOH6XEVWLWXWLRQUHDFWLRQFRQYHUVLRQRIDON\OKDOLGHVWRDON\OD]LGHV Similar to: /LWKLXP /L SRWDVVLXP .
([DPSOH5HGXFWLRQFRQYHUVLRQRIDON\QHVWRtrans alkenes
Dimethyl sulfoxide
(DMSO) is a common
solvent for SN2 reactions
Example 2: Conversion of alcohols to alkoxides
([DPSOH&XUWLXVUHDUUDQJHPHQWDF\OKDOLGHVWRDPLQHV
([DPSOH%LUFKUHGXFWLRQFRQYHUVLRQRIDUHQHVWRGLHQHV
How it works: Nucleophilic substitution

6RGLXPD]LGHLVWKHFRQMXJDWHEDVHRIWKHZHDNDFLG+13 S.D ,WLVDQH[- How it works: Reduction of alkynes to trans-alkenes
FHOOHQWQXFOHRSKLOHWKDWKDSSHQVWREHDZHDNEDVHUHDFWLRQVXVLQJ13ZLOOKDYH
6RGLXPPHWDOKDVDQH[WUHPHO\ORZLRQL]DWLRQHQHUJ\DQGZLOOUHDGLO\JLYH
YHU\OLWWOHFRPSHWLWLRQIURPHOLPLQDWLRQSDWKZD\V
XSLWVHOHFWURQ
not covered in Org 1/

Org 2, but these types
How it works: Curtius rearrangement of radicals can easily
6RGLXPD]LGHUHDFWVZLWKWKHDF\OKDOLGHWRIRUPDQDF\OD]LGHYLDDWZRVWHS The preference interconvert between
DGGLWLRQHOLPLQDWLRQSURFHVV for trans geometry geometries
can be explained
by the fact that
Addition Elimination these anions repel
each other such Protonation (by The solvent in these
Acyl azide that they maximize solvent) types of reactions is
their distance
8SRQKHDWLQJWKHQHLJKERULQJFDUERQPLJUDWHVWRQLWURJHQLQDVKLIWOHDGLQJ apart
ammonia (NH3)
WRORVVRI1DQGIRUPDWLRQRIDQLVRF\DQDWH$GGLWLRQRIZDWHUWRWKHLVRF\DQDWH
PHFKDQLVPQRWVKRZQ IROORZHGE\GHFDUER[\ODWLRQOHDGVWRDQDPLQH
Trans alkene
Isocyanate
Amine
Index Index
84 85
5H 5H)/4
JVU[PU\LK :VKP\TIVYVO`KYPKL
How it works: The Birch Reduction :KDWLW·VXVHGIRU6RGLXPERURK\GULGHLVDUHDJHQWPDLQO\XVHGIRUWKHUHGXF-

7KH%LUFKUHGXFWLRQLVDPHWKRGIRUWUDQVIRUPLQJDURPDWLFULQJVLQWRGLHQHV7KH WLRQRINHWRQHVDQGDOGHK\GHV LWZLOODOVRUHGXFHDFLGKDOLGHV ,WLVDOVRXVHGLQ
SURGXFWVREWDLQHGGHSHQGRQWKHVXEVWLWXHQW(OHFWURQGRQDWLQJJURXSVSURYLGH WKHR[\PHUFXUDWLRQRIDONHQHVWRUHSODFHPHUFXU\ZLWK+
SURGXFWVZKHUHWKHDONHQHLVDWWDFKHGWRWKHHOHFWURQGRQDWLQJJURXS HQROHWKHUV
Similar to:/LWKLXPDOXPLQXPK\GULGH /L$O+4 EXWOHVVUHDFWLYH$OVRVLPLODUWR
RWKHUUHGXFLQJDJHQWVVXFKDV1D&1%+3',%$//L$O+ 2W%X 3HWF
([DPSOH5HGXFWLRQFRQYHUVLRQRINHWRQHVWRVHFRQGDU\DOFRKROV
When an electron donating group

such as OMe is present, protonation
occurs on the meta position
Example 2: Reduction of aldehydes to primary alcohols
([DPSOH2[\PHUFXUDWLRQFRQYHUVLRQRIDONHQHVWRDOFRKROV
The alcohol need not be t-BuOH; ethanol
(EtOH), methanol (MeOH) and isopropa-
nol (iPrOH) are all effective.
:KHQHOHFWURQZLWKGUDZLQJVXEVWLWXHQWVDUHSUHVHQWSURWRQDWLRQRFFXUVRQWKH
FDUERQDGMDFHQWWRWKHHOHFWURQZLWKGUDZLQJJURXS How it works: Reductions of aldehydes and ketones
6RGLXPERURK\GULGHLVDJRRGUHGXFLQJDJHQW$OWKRXJKQRWDVSRZHUIXODV
/L$O+4LWLVYHU\HIIHFWLYHIRUWKHUHGXFWLRQRIDOGHK\GHVDQGNHWRQHVWRDOFRKROV
,WZLOOJHQHUDOO\QRWUHGXFHHVWHUVRUDPLGHV
Note that protonation

occurs adjacent to
Addition
the electron with-
drawing group
Protonation This reaction is

commonly performed
in a solvent such
as CH3OH, which
serves as a source of
protons.

Index Index
86 87
5H)/4 5H)/6(J3
JVU[PU\LK Sodium triacetoxy
IVYVO`KYPKL
How it works: In the oxymercuration reaction
,QWKHR[\PHUFXUDWLRQUHDFWLRQ1D%+4LVXVHGWREUHDNWKHFDUERQPHUFXU\
ERQGDQGUHSODFHLWZLWKK\GURJHQ VHFRQGVWHS :KDWLW·VXVHGIRU6RGLXPWULDFHWR[\ERURK\GULGHLVDUHGXFLQJDJHQW,WLVPRVW
RIWHQXVHGIRUWKHUHGXFWLYHDPLQDWLRQRINHWRQHV DQGDOGHK\GHV WRDPLQHV,Q
WKLVUHVSHFWLWLVLGHQWLFDOWRVRGLXPF\DQRERURK\GULGH 1D&1%+3 5HGXFWLRQLV
RIWHQSHUIRUPHGXQGHUPLOGO\DFLGLFFRQGLWLRQV
Similar to:1D&1%+31D%+4
([DPSOH5HGXFWLYHDPLQDWLRQFRQYHUVLRQRIDOGHK\GHVWRDPLQHV
7KHPHFKDQLVPIRUWKLVSURFHVVLVrarely covered in textbooksEXWLVFRYHUHG

KHUHIRUWKHVDNHRIFRPSOHWHQHVV
([DPSOH5HGXFWLYHDPLQDWLRQFRQYHUVLRQRINHWRQHVWRDPLQHV
The C3Hg bond is weakened

Hydride attacks Hg, displacing and breaks homolytically to
the acetate ion give a carbon radical
How it works: Reductive amination

The carbon radical then
abstracts hydrogen from 5HGXFWLYHDPLQDWLRQZLWK1D%+ 2$F 3ZRUNVHVVHQWLDOO\WKHVDPH
the resulting Hg(I), giving ZD\DVLWGRHVIRUVRGLXPF\DQRERURK\GULGH 1D%+3&1
Net result is replacement of elemental mercury as a
mercury for hydrogen. product.
7KHGHXWHUDWHGYHUVLRQRI1D%+4VRGLXPERURGHXWHULGH 1D%'4 ZLOO

UHSODFH+JZLWK'

Index Index
88 89
5H*5)/3 5H/
:VKP\TJ`HUVIVYVO`KYPKL Sodium Hydride
:KDWLW·VXVHGIRU6RGLXPF\DQRERURK\GULGHLVDUHGXFLQJDJHQW,WLVJHQHUDOO\ :KDWLW·VXVHGIRU6RGLXPK\GULGHLVDVWURQJEDVHDQGDSRRUQXFOHRSKLOH,WLV
XVHGIRUUHGXFWLYHDPLQDWLRQWKHUHGXFWLRQRILPLQHV RU´LPLQLXPVµ WRDPLQHV XVHIXOIRUGHSURWRQDWLQJDOFRKROVDQGDON\QHVDPRQJRWKHUV2QHDGYDQWDJHRI
,W·VFRPPRQWRSHUIRUPWKLVUHDFWLRQXQGHUVOLJKWO\DFLGLFFRQGLWLRQV S+ XVLQJ1D+LVWKDWWKHE\SURGXFWLV+DJDVZKLFKGRHVQRWIXUWKHULQWHUIHUHZLWK
WKHUHDFWLRQ
Similar to:1D%+41D%+ 2$F 3
Similar to:3RWDVVLXPK\GULGH .+ OLWKLXPK\GULGH /L+
([DPSOH5HGXFWLYHDPLQDWLRQFRQYHUVLRQRINHWRQHVWRDPLQHV
([DPSOH$FLGEDVHUHDFWLRQFRQYHUVLRQRIDON\QHVWRDFHW\OLGHV
([DPSOH5HGXFWLYHDPLQDWLRQFRQYHUVLRQRIDOGHK\GHVWRDPLQHV ([DPSOH$FLGEDVHUHDFWLRQFRQYHUVLRQRIDOFRKROVWRDONR[LGHV
Example 3: Deprotonation of phosphonium salts to form ylides
How it works: Reductive amination

7KHÀUVWVWHSLVIRUPDWLRQRIDQLPLQHIURPWKHDOGHK\GHNHWRQHDQGWKHDPLQH
How it works: Deprotonation
+²LVDVWURQJEDVHWKHFRQMXJDWHEDVHRIK\GURJHQ S.D
imine ,WZLOOUHDGLO\GHSURWRQDWHDOFRKROV S.D DON\QHV S.D DQG

RWKHUVSHFLHVWKDWDUHPRUHDFLGLFWKDQK\GURJHQ
$WS+DVLJQLÀFDQWSURSRUWLRQRIWKHLPLQHLVSUHVHQWDVLWVFRQMXJDWHDFLG
´LPLQLXPµ ZKLFKLVDPRUHUHDFWLYHHOHFWURSKLOHWKDQWKHLPLQH 2QHDGYDQWDJHRIXVLQJ1D+ DQG.+ LVWKDWWKHFRQMXJDWHDFLGLVDJDV
+ DQGZLOOEXEEOHRXWRIWKHUHDFWLRQYHVVHOQRWLQWHUIHULQJZLWKWKHUHDF-
WLRQIXUWKHU7KLVDOVRPHDQVWKDWWKHGHSURWRQDWLRQLVLUUHYHUVLEOH
iminium
)RUPRVWSXUSRVHVLWFDQEHXVHGLQWHUFKDQJDEO\ZLWK1D1+DQGRWKHU
imine
amine VWURQJEDVHV
,QWHUHVWLQJO\1D&1%+3LVDSRRUHUUHGXFLQJDJHQWWKDQ1D%+4,WLVXVHG
EHFDXVHDWVOLJKWO\DFLGLFS+ a LWLVVHOHFWLYHIRUUHGXFLQJLPLQLXPLRQV WKH
FRQMXJDWHDFLGVRILPLQHV RYHUDOGHK\GHVDQGNHWRQHV
7KHSURFHVVRIFRQYHUWLQJDNHWRQHRUDOGHK\GHWRDQDPLQHLQWKHSUHVHQFHRI
DUHGXFLQJDJHQWVXFKDV1D%+3&1LVFDOOHGÚHGXFWLYHDPLQDWLRQµ

Index Index
90 91
5H064 5H5/2
Sodium periodate Sodium amide
:KDWLW·VXVHGIRU6RGLXPSHULRGDWHLVDVWURQJR[LGDQW,WZLOOFOHDYHGLROV Also known as:6RGDPLGH

YLFLQDOGLROV WRJLYHDOGHK\GHVDQGNHWRQHV
:KDWLW·VXVHGIRU6RGLXPDPLGHLVDYHU\VWURQJEDVHXVHIXOIRUWKHGHSURWRQ-
Similar to:3HULRGLFDFLG +,24 /HDG ,9 DFHWDWH>3E 2$F 4@ DWLRQRIDON\QHVDQGDOVRLQHOLPLQDWLRQUHDFWLRQVWRZDUGWKHIRUPDWLRQRIDON\QHV
([DPSOH2[LGDWLYHFOHDYDJHFRQYHUVLRQRIGLROVWRDOGHK\GHVNHWRQHV IURPGLKDOLGHV,WFDQDOVREHXVHGWRJHQHUDWHDU\QHV ÉHQ]\QHVµ ZKLFKFDQ
XQGHUJRQXFOHRSKLOLFDWWDFN
Similar to:/L1+.1+(VVHQWLDOO\WKHVDPHEDVHVWUHQJWKDV/'$DOWKRXJKOHVV
VWHULFDOO\KLQGHUHG
([DPSOH$FLGEDVHUHDFWLRQFRQYHUVLRQRIDON\QHVWRDFHW\OLGHV
([DPSOH(OLPLQDWLRQFRQYHUVLRQRIJHPLQDOGLKDOLGHVWRDON\QHV
How it works: Oxidative cleavage of diols to give aldehydes/ketones
<Geminal= dihalide -
has two halogens on
the same carbon
([DPSOH$FLGEDVHUHDFWLRQFRQYHUVLRQRIYLFLQDOGLKDOLGHVWRDON\QHV
Attack of oxygen <Vicinal= dihalide -
on iodine (followed has two halogens on
Attack of second oxygen
by proton transfer) adjacent carbons
on iodine (followed by
another proton transfer)
([DPSOH&RQYHUVLRQRIDU\OKDOLGHVWRDU\ODPLQHV YLDDU\QHV
Key oxidative
cleavage step! This proceeds
through an aryne
mechanism
How it works: As a strong base
1D1+LVWKHFRQMXJDWHEDVHRIDPPRQLD S.D ,WLVVXIÀFLHQWO\VWURQJWR
Trivial detail: this usually loses GHSURWRQDWHDON\QHVZKLFKFDQQRWEHGRQHUHOLDEO\ZLWK1D2+
water to give NaIO3 plus H2O 1D1+LVDOVRDXVHIXOUHDJHQWIRUSHUIRUPLQJWKHHOLPLQDWLRQRIJHPLQDOGLKDOLGHV
WRDON\QHV
1RWHWKDWLQWKLVSURFHVVLRGLQH 9,, KDVEHHQUHGXFHGWRLRGLQH 9

Index Index
92 93
5H6/
Base
Sodium hydroxide
5H6,[
Sodium Ethoxide
:KDWLW·VXVHGIRU+\GUR[LGHLRQ RIWHQHQFRXQWHUHGDV1D2+RU.2+ LVD
VWURQJEDVHDQGJRRGQXFOHRSKLOH,WLVLPSRVVLEOHWRPHQWLRQDOORILWVDSSOLFDWLRQV
KHUHEXWDIHZRILWVFUXFLDOUHDFWLRQVDUHKLJKOLJKWHG Also known as:1D2&+&+3
:KDWLW·VXVHGIRU6WURQJEDVHDQGJRRGQXFOHRSKLOH0RVWRIWHQVHHQDVD
Similar to:6LPLODULQDFWLRQWRRWKHUVWURQJEDVHV
EDVHIRUSURPRWLQJHOLPLQDWLRQUHDFWLRQV ( &DQDOVREHXVHGDVDQXFOHRSKLOH
([DPSOH$FLGEDVHUHDFWLRQFRQYHUVLRQRIDOFRKROVWRDONR[LGHV LQ6NUHDFWLRQVSDUWLFXODUO\LIWKHDON\OKDOLGHLVSULPDU\
7KHFRQMXJDWHEDVHRIHWKDQRO1RWUHDOO\DÚHDJHQWµSHUVHEXWJHWVVRPXFK
XVHWKDWLWGHVHUYHVLWVRZQHQWU\
Equivalent to.2(W/L2(W²2(W6LPLODUWR1D20H 1D2&+3
([DPSOH(OLPLQDWLRQFRQYHUVLRQRIDON\OKDOLGHVWRDONHQHV
1RWHWKDW1D2(WLVQRWUHDOO\DÚHDJHQWµLW·VDQRUJDQLFPROHFXOH7KHH[DPSOHV
VKRZQEHORZDUHLOOXVWUDWLYHEXWIDUIURPFRPSUHKHQVLYH
([DPSOH(OLPLQDWLRQRIDON\OKDOLGHV (
E2 mechanism.
([DPSOH$FLGEDVHUHDFWLRQFRQYHUVLRQRINHWRQHVDOGHK\GHVWRHQRODWHV Hydrogen and leaving
group (Br) must be
<anti= . Heat helps to
promote elimination.
([DPSOH6XEVWLWXWLRQ 6N2) of alkyl halides
([DPSOH6XEVWLWXWLRQFRQYHUVLRQRIDON\OKDOLGHVWRDOFRKROV
works best for primary
alkyl halides. With sec-
ondary, E2 competes
([DPSOH$F\OVXEVWLWXWLRQFRQYHUVLRQRIDF\OKDOLGHVWRFDUER[\OLFDFLGV Example 3: Reaction with acyl halides to form esters

Also works for anhydrides
([DPSOH$F\OVXEVWLWXWLRQ VDSRQLÀFDWLRQ FRQYHUVLRQRIHVWHUVWR

carboxylic acids How it works: E2 Reaction
Note <anti= relationship of
H and Br
([DPSOH$F\OVXEVWLWXWLRQFRQYHUVLRQRIDQK\GULGHVWRFDUER[\OLFDFLGV
triple line means

<same as=
Same reaction,
drawn as chair

Index Index
94 95
5): 5):
NÐBromosuccinimide JVU[PU\LK
How it works: Allylic bromination

:KDWLW·VXVHGIRU1%6LVDVRXUFHRIUHDFWLYHHOHFWURSKLOLFEURPLQH,WLVRIWHQ 1%6SURYLGHVDFRQVWDQWORZFRQFHQWUDWLRQRI%UZKLFKLVIRUPHGZKHQ+%U
XVHGIRUDOO\OLFEURPLQDWLRQDQGLQIRUPDWLRQRIKDORK\GULQVIURPDONHQHV6LQFHLW IURPSURSDJDWLRQVWHS UHDFWVZLWK1%67KLVLVXVHIXOEHFDXVHWKHORZFRQ-
LVDFU\VWDOOLQHVROLGLWLVPRUHFRQYHQLHQWWRXVHWKDQOLTXLGHOHPHQWDO%U FHQWUDWLRQRI%USUHYHQWVGLEURPLQDWLRQRIWKHGRXEOHERQGIURPRFFXULQJ
Similar to:%U1&6 NFKORURVXFFLQLPLGH 1,6 NLRGRVXFFLQLPLGH Generation of Br2
([DPSOH$OO\OLFEURPLQDWLRQFRQYHUVLRQRIDONHQHVWRDOO\OLFEURPLGHV
This byproduct is
called <succinimide=
Initiation step
Example 2: Conversion of alkenes to bromohydrins :KHQEURPLQHLVKHDWHGRUWUHDWHGZLWKOLJKWKRPRO\WLFFOHDYDJHRIWKH%U²%U

ERQGUHVXOWVLQWKHIRUPDWLRQRIWZREURPLQHUDGLFDOV
Propagation step 1
,QWKHÀUVWSURSDJDWLRQVWHSWKHEURPLQHUDGLFDOUHPRYHVDK\GURJHQIURPWKH
Bromohydrin DOO\OLFFDUERQJLYLQJDUHVRQDQFHVWDELOL]HGIUHHUDGLFDO
How it works: Halohydrin formation

$VZLWK%UDONHQHVWUHDWHGZLWK1%6ZLOOIRUPEURPRQLXPLRQV
Propagation step 2
,QWKHVHFRQGSURSDJDWLRQVWHSWKHDOO\OLFUDGLFDOUHDFWVZLWK%UJLYLQJWKHDOO\OLF
EURPLGHDQGUHJHQHUDWLQJDQHZ%UUDGLFDO7KLVFRQWLQXHVWKHFDWDO\WLFF\FOH
Trans product
Bromonium ion formation
7KHWUDQVSURGXFWLVIRUPHGH[FOXVLYHO\GXHWRDWWDFNRIQXFOHRSKLOHRQWKHIDFH
RSSRVLWHWKHEURPRQLXPLRQ1RWHLQWKLVFDVHDPL[WXUHRIHQDQWLRPHUVLV
IRUPHG
Top view
Side view
+ succinimide
Attack by solvent
(water in this case) Deprotonation

(Enantiomer)
2
Index Index
96 97
5*: 50:
NÐ*OSVYV:\JJPUPTPKL NÐIodo Succinimide
:KDWLW·VXVHGIRU1FKORURVXFFLQLPLGHLVDVRXUFHRIUHDFWLYH HOHFWURSKLOLF :KDWLW·VXVHGIRU1LRGRVXFFLQLPLGHLVDVRXUFHRIHOHFWURSKLOLFLRGLQHVLPLODU

FKORULQH,WLVXVHGIRUWKHIRUPDWLRQRIFKORURK\GULQVIURPDONHQHV$FU\VWDOOLQH WR1%6DQG1&6:KHQDGGHGWRDQDONHQHLQWKHSUHVHQFHRIZDWHULWZLOOIRUP
VROLGLWLVPRUHHDVLO\KDQGOHGWKDQGDQJHURXVFKORULQHJDV LRGRK\GULQV
Similar to: I1%61&6
Similar to: &ONEURPRVXFFLQLPLGH 1%6 NLRGRVXFFLQLPLGH 1,6
Example 1: Conversion of alkenes to chlorohydrins Example 1: Conversion of alkenes to iodohydrins
How it works: Iodohydrin formation

How it works: Formation of chlorohydrins 7KHUHDFWLRQSURFHHGVYLDDWWDFNRIWKHDONHQHXSRQWKHLRGLQHIROORZHGE\
7KHÀUVWVWHSLQFKORURK\GULQIRUPDWLRQLVDWWDFNRIWKHQXFOHRSKLOLFDONHQHXSRQ DWWDFNRIQXFOHRSKLOLFVROYHQWXSRQWKHLRGRQLXPLRQ
WKHHOHFWURSKLOLFFKORULQH7KLVIRUPVDQLQWHUPHGLDWHFKORURQLXPLRQ,QWKH
SUHVHQFHRIDQXFOHRSKLOLFVROYHQWVXFKDV+2WKLVFKORURQLXPLRQLVDWWDFNHG
WRJLYHWKHFKORURK\GULQ
Iodonium ion
6LQFHDWWDFNRQWKHLRGRQLXPLRQRFFXUVH[FOXVLYHO\IURPWKHEDFNVLGHWKH
WUDQVSURGXFWLVIRUPHGH[FOXVLYHO\
Chloronium ion
6LQFHDWWDFNRQWKHFKORURQLXPLRQRFFXUVH[FOXVLYHO\IURPWKHEDFNVLGH
WKHWUDQVSURGXFWLVIRUPHGH[FOXVLYHO\
,IRWKHUQXFOHRSKLOLFVROYHQWVDUHXVHG HJDOFRKROV HWKHUVZLOOEH

IRUPHG7KLVLVDQH[DPSOHRILRGRHWKHULÀFDWLRQ
Note - the
enantiomer is
also formed
here

Index Index
98 99
5/2OH 5/3
/`KYV_`SHTPUL Ammonia
:KDWLW·VXVHGIRU+\GUR[\ODPLQHLVDJRRGQXFOHRSKLOH,WLVPRVWFRPPRQO\ Also known as:1+3 O VLJQLÀHVLWLVDOLTXLG

XVHGIRUWKHIRUPDWLRQRIR[LPHVDSUHFXUVRUWRWKH%HFNPDQQUHDUUDQJHPHQW
:KDWLW·VXVHGIRU$PPRQLDLVDEDVHDQGDQXFOHRSKLOH,WLVRIWHQXVHGDVD
Example 1: Conversion of ketones/aldehydes to oximes VROYHQWLQUHDFWLRQVLQYROYLQJOLWKLXP /L VRGLXP 1D DQGSRWDVVLXP . ,WKDV
TXLWHDORZERLOLQJSRLQW ²R&
([DPSOH$VDVROYHQWFRQYHUVLRQRIDON\QHVWRDFHW\OLGHV
Oxime
([DPSOH%HFNPDQQUHDUUDQJHPHQWFRQYHUVLRQRIR[LPHVWRDPLGHV
([DPSOH$VDQXFOHRSKLOHFRQYHUVLRQRIDF\OFKORULGHVWRDPLGHV
How it works: Conversion of ketones/aldeydes to oximes

How it works:
7UHDWPHQWRIDQDOGHK\GHRUNHWRQHZLWK1+2+OHDGVWRIRUPDWLRQRIDQR[LPH 1+3LVWKHVLPSOHVWDPLQHDQGLVD/HZLVEDVHGXHWRLWVXQVKDUHGORQHSDLU
0LOGDFLG DOWKRXJKQRWVKRZQ FDQDFFHOHUDWHWKLVUHDFWLRQ RIHOHFWURQV
Proton %HLQJWKHFRQMXJDWHDFLGRI1D1+LWLVWKHSHUIHFWVROYHQWIRUWKLVEDVH
transfer PXFKOLNH0H2+LVXVHGDVDVROYHQWIRU1D20H
Addition
Elimination
Oxime
Deprotonation
How it works: Beckmann rearrangement

7UHDWPHQWRIWKHR[LPHZLWKDFLGDQGKHDWOHDGVWRDUHDUUDQJHPHQWRFFXUULQJ
VLPXOWDQHRXVO\ZLWKORVVRIZDWHU7KHSURGXFWLVDQLWULOH
Protonation Rearrangement
Oxime
Deprotonation
@bohring_bot
Nitrile

Index Index
100 101
5/25/2 5P2B
/`KYHaPUL 5PJRLSIVYPKL
:KDWLW·VXVHGIRU+\GUD]LQHLVDJRRGUHGXFWDQWDQGQXFOHRSKLOH,WLVXVHGLQ :KDWLW·VXVHGIRU1LFNHOERULGHLVDUHGXFLQJDJHQWXVHGIRUWKHUHGXFWLRQRI
WKH:ROII.LVKQHUUHDFWLRQDPHDQVRIFRQYHUWLQJNHWRQHVWRDONDQHV,WLVDOVR DON\QHVWRJLYHcisDONHQHV
XVHGLQWKHÀQDOVWHSRIWKH*DEULHODPLQHV\QWKHVLVWROLEHUDWHWKHIUHHDPLQH
Similar to: /LQGODU·VFDWDO\VW
([DPSOH:ROII.LVKQHUUHDFWLRQFRQYHUVLRQRINHWRQHVWRDONDQHV
([DPSOH5HGXFWLRQFRQYHUVLRQRIDON\QHVWRDONHQHV
How it works: Partial reduction of alkynes.
([DPSOH*DEULHOV\QWKHVLVFRQYHUVLRQRISKWKDOLPLGHWRSULPDU\DPLQH 1LFNHOERULGHLVJHQHUDOO\IRUPHGLQWKHUHDFWLRQYHVVHOE\DGGLQJ1D%+4
WRQLFNHO ,, VDOWVVXFKDV1L&O,WEHKDYHVWKHVDPHDV/LQGODU·VFDW-
DO\VWSHUIRUPLQJSDUWLDOK\GURJHQDWLRQRIDON\QHVWRJLYHDONHQHV7KH
VWHUHRFKHPLVWU\LVDOZD\Vsyn
,WFDQDOVREHXVHGLQWKHSUHVHQFHRIK\GURJHQJDVDVLQWKHH[DPSOH
DERYH
How it works: The Wolff-Kishner reaction
+\GUD]LQHOLNHRWKHUDPLQHVZLOODGGWRDOGHK\GHVDQGNHWRQHVWRIRUPFRQGHQ-
1LFNHOERULGHGRHVQRWUHDFWZLWKDONHQHV
VDWLRQSURGXFWV7KHLPLQHRIK\GUD]LQHLVFDOOHGD´K\GUD]RQHµ
hydrazone
:KHQWUHDWHGZLWKVWURQJEDVHDQGKHDWHGYLJRURXVO\QLWURJHQJDVLVOLEHUDWHG
DQGDQDONDQHLVIRUPHG7KLVLVWKH:ROII.LVKQHUUHDFWLRQ
Deprotonation
Resonance Protonation
Although this species is often

drawn in the mechanism, it Protonation
likely does not exist as
the free carbanion. Deprotonation
Alkane
Index Index
102 103
O3 or O3
6aVUL JVU[PU\LK
:KDWLW·VXVHGIRU2]RQHLVDQR[LGL]LQJDJHQW,WZLOOFOHDYHDONHQHVDQGDON\QHV How it works: Reductive workup

WRJLYHFDUERQ\OFRPSRXQGVLQDUHDFWLRQFDOOHG´R[LGDWLYHFOHDYDJHµ7KHSURGXFWV
'LPHWK\OVXOÀGHLVDUHGXFLQJDJHQW,WEUHDNVWKHZHDN2²2ERQGDQG
IRUPHGFDQEHGHSHQGHQWRQWKHW\SHRIZRUNXSXVHG5HGXFWLYHZRUNXSSUHVHUYHV
H[SHOVGLPHWK\OVXOIR[LGH '062
DOGHK\GHVZKHUHDVR[LGDWLYHZRUNXSZLOOR[LGL]HDQ\DOGHK\GHVWRFDUER[\OLF
DFLGV
Similar to: .0Q24
([DPSOH2[LGDWLYHFOHDYDJH UHGXFWLYHZRUNXS FRQYHUVLRQRIDONHQHV
to aldehydes/ketones
DMSO
How it works: Oxidative workup

+\GURJHQSHUR[LGHR[LGL]HVDOGHK\GHVWRFDUER[\OLFDFLGV8SRQZDUPLQJWKH
([DPSOH2[LGDWLYHFOHDYDJH R[LGDWLYHZRUNXS FRQYHUVLRQRIDONHQHV R]RQLGHRSHQVXSWRDQDOGHK\GHDQGFDUERQ\OR[LGHZKLFKDUHFRQYHUWHGWR
to carboxylic acids/ketones FDUER[\OLFDFLGV
([DPSOH2[LGDWLYHFOHDYDJHFRQYHUVLRQRIDON\QHVWRFDUER[\OLFDFLGV Ozonide (decomposes Addition

upon warming)
How it works: Oxidative cleavage of alkenes

7UHDWPHQWRIDQDONHQHZLWKR]RQHOHDGVWRLQLWLDOIRUPDWLRQRIDPROR]RQLGH Proton
IROORZHGE\UHDUUDQJHPHQWWRDQR]RQLGH5HGXFWLRQJLYHVWKHFDUERQ\OSURGXFWV transfer
Deprotonation Trivial detail - the deprotonation step

is rate-limiting, so the reaction can
<Molozonide= be accelerated by the addition of a
base such as NaOH
Reduction

Index Index
104 105
R2CuLi RLi
Organocuprates 6YNHUVSP[OP\TYLHNLU[Z
Also known as:*LOPDQUHDJHQWV :KDWLW·VXVHGIRU2UJDQROLWKLXPUHDJHQWVDUHH[WUHPHO\VWURQJEDVHVDQGJRRG

QXFOHRSKLOHVWKH\UHDFWZLWKFDUERQ\OFRPSRXQGV DOGHK\GHVNHWRQHVHVWHUVHWF
:KDWLW·VXVHGIRU2UJDQRFXSUDWHUHDJHQWV *LOPDQUHDJHQWV DUHFDUERQQXF- DQGHSR[LGHV%HLQJVWURQJEDVHVWKH\ZLOODOVRUHDFWZLWKJURXSVFRQWDLQLQJDFLGLF
OHRSKLOHV7KH\ZLOOSHUIRUP>@DGGLWLRQV ´FRQMXJDWHDGGLWLRQVµ WR_`XQVDWX- K\GURJHQV
UDWHGNHWRQHVDVZHOODV6NUHDFWLRQVZLWKFHUWDLQW\SHVRIDON\OKDOLGHV7KH\
FDQDOVRDGGWRDF\OKDOLGHVWRJLYHNHWRQHV Similar to:*ULJQDUGUHDJHQWV
Similar to: *ULJQDUGUHDJHQWVRUJDQROLWKLXPUHDJHQWV Example 1: Conversion of alkyl halides to organolithiums
Example 1: Conversion of alkyllithiums to organocuprates
Example 2: Conversion of aldehydes to secondary alcohols

Acid is added in the
second step to protonate
([DPSOH&RQMXJDWHDGGLWLRQDGGLWLRQWR_, ` unsaturated ketones
the negatively charged
This reaction works best oxygen
for methyl, allyl, and benzyl
halides Example 3: Conversion of ketones to tertiary alcohols
Acid is added in the
second step to protonate
([DPSOH6XEVWLWXWLRQFRQYHUVLRQRIDON\OKDOLGHVWRDONDQHV 6N2) the negatively charged
oxygen
Example 4: Conversion of esters to tertiary alcohols

Organolithium reagents
add twice to esters,
acid halides, and anhy-
drides
Example 5: Conversion of acyl halides to tertiary alcohols

([DPSOH$F\OVXEVWLWXWLRQFRQYHUVLRQRIDF\OKDOLGHVWRNHWRQHV add twice to esters,
acid halides, and anhy-
drides
([DPSOH(SR[LGHRSHQLQJFRQYHUVLRQRIHSR[LGHVWRDOFRKROV
How it works: As a nucleophile
add to the less substituted
end of epoxides. Acid is
Electronegativity Due to carbon9s higher electronegativity
added to protonate the
& relative to Cu, it bears a partial positive
negatively charged oxygen.
&X charge and is thus nucleophilic.

Index Index
106 107
RÐLi RÐLi
JVU[PU\LK JVU[PU\LK
Example 7: Reaction with carbon dioxide How it works: Addition to esters / acid halides / anhydrides
2UJDQROLWKLXPUHDJHQWVDGGWZLFHWZRWKHVHJURXSV7KHUHDFWLRQSURFHHGV
WKURXJKDGGLWLRQHOLPLQDWLRQDQGDVHFRQGDGGLWLRQ$GGLWLRQRIDFLGDWWKHHQG
SURYLHVDQHXWUDOWHUWLDU\DOFRKRO
Example 8: Formation of organocuprates
Addition
Example 9: As a base
Elimination of alkoxide
Organolithium reagents provides a ketone
are extremely strong
bases.
A second addition of
organolithium reagent
then occurs on to the
new ketone
Example 10: Addition to carboxylic acids Organolithium reagents
can add to carboxylic
acids if 2 equivalents
Addition of acid gives
are added. HX the neutral tertiary
How it works: Addition to aldehydes/ketones alcohol
2UJDQROLWKLXPUHDJHQWVDUHH[WUHPHO\VWURQJQXFOHRSKLOHV7KHHOHFWURQVLQ
WKH&²/LERQGDUHKLJKO\SRODUL]HGWRZDUGFDUERQ
behaves much like
How it works: Addition to epoxides

2UJDQROLWKLXPUHDJHQWVUHDGLO\DGGWRWKHHOHFWURSKLOLFFDUERQ\ODWRPLQ
DOGHK\GHVDQGNHWRQHV6XEVHTXHQWDGGLWLRQRIDFLGJLYHVWKHQHXWUDO 2UJDQROLWKLXPUHDJHQWVDGGWRWKHOHDVWKLQGHUHGHQGRIHSR[LGHV \RX
DOFRKRO FDQWKLQNRIWKLVOLNHDQ6N 3URWRQDWLRQWKHQJLYHVWKHQHXWUDODOFRKRO
Addition Protonation
Addition Protonation

Index Index
108 109
OsO4 7I6(J4
Osmium tetroxide Lead tetraacetate
Also known as:/HDG ,9 DFHWDWH
:KDWLW·VXVHGIRU2VPLXPWHWUR[LGHLVDUHDJHQWIRUWKHIRUPDWLRQRIGLROV :KDWLW·VXVHGIRU/HDGWHWUDDFHWDWHZLOOFOHDYHGLROV YLFLQDOGLROV LQWRDOGH-

YLFLQDOGLROV IURPDONHQHV7KHVHOHFWLYLW\IRUWKLVUHDFWLRQLVDOZD\Vsyn K\GHVNHWRQHVVLPLODUWR1D,24DQG+,24
Similar to:.0Q24 FROGGLOXWH Similar to:6RGLXPSHULRGDWH 1D,24 SHULRGLFDFLG +,24
([DPSOH2[LGDWLYHFOHDYDJHFRQYHUVLRQRIGLROVWRDOGHK\GHVNHWRQHV
([DPSOH'LK\GUR[\ODWLRQFRQYHUVLRQRIDONHQHVWRJLYHYLFLQDOGLROV
The stereochemistry of
this reaction is always
<syn=
In the lab, KHSO3 helps to remove the

osmium from this reaction. Its pres- How it works: Cleavage of diols to aldehydes/ketones
FODFIBTOPFGGFDUPOUIFmOBMQSPEVDU
(as shown here) /HDG ,9 DFHWDWHLVDQR[LGL]LQJDJHQW,WZRUNVE\FRRUGLQDWLQJWRWKH
GLRODQGWKHQEUHDNLQJWKHFDUERQFDUERQERQGLQDF\FOLFPHFKDQLVP
How it works: Dihydroxylation of alkenes
2[\JHQVERWKDSSURDFKWKHDONHQHIURP (formed after proton

WKHVDPHIDFH transfer)
Coordination
6RPHWLPHV1D+623RU.+623 ELVXOÀWH
LVDGGHGWREUHDNGRZQWKHF\FOLFRVPLXP Coordination (and subsequent
FRPSRXQGLQWRDGLRODQGDQRVPLXPVDOW proton transfer)
Oxidative
cleavage
1RWHWKDW3E ,9 KDVEHHQUHGXFHGWR3E ,, 7KHDFHWDWHJURXSVDUHOLEHUDWHG

DVDFHWLFDFLG

Index Index
110 111
PBr3 7*S3
7OVZWOVY\Z[YPIYVTPKL 7OVZWOVY\Z[YPJOSVYPKL
:KDWLW·VXVHGIRU3KRVSKRUXVWULEURPLGHLVDUHDJHQWIRUFRQYHUWLQJDOFRKROV :KDWLW·VXVHGIRU3KRVSKRUXVWULFKORULGHLVDUHDJHQWIRUWKHFRQYHUVLRQRI
WRDON\OEURPLGHV,WZLOODOVRFRQYHUWFDUER[\OLFDFLGVWRDFLGEURPLGHV DF\O DOFRKROVWRDON\OFKORULGHV,WZLOODOVRFRQYHUWFDUER[\OLFDFLGVWRDFLGFKORULGHV
EURPLGHV DF\OFKORULGHV
Similar to:7KLRQ\OEURPLGH 62%U Similar to:62&O3&O0HFKDQLVPVH[DFWO\WKHVDPHDVIRU3%U3
([DPSOH6XEVWLWXWLRQFRQYHUVLRQRIDOFRKROVWRDON\OEURPLGHV ([DPSOH6XEVWLWXWLRQFRQYHUVLRQRIDOFRKROVWRDON\OFKORULGHV
([DPSOH$F\OVXEVWLWXWLRQFRQYHUVLRQRIFDUER[\OLFDFLGVWRDF\O ([DPSOH$F\OVXEVWLWXWLRQFRQYHUVLRQRIFDUER[\OLFDFLGVWRDF\O
bromides chlorides
How it works: Formation of alkyl bromides from alcohols How it works: Formation of alkyl chlorides from alcohols
3KRVSKRUXVWULEURPLGHLVXVHIXOIRUFRQYHUWLQJDOFRKROVLQWRDON\OEURPLGHVZLWK
LQYHUVLRQRIFRQÀJXUDWLRQ'ULYLQJIRUFHLVIRUPDWLRQRIWKHVWURQJ3 2ERQG
How it works: Formation of acyl bromides How it works: Formation of acyl chlorides from carboxylic acids
Attack of oxygen Addition Attack of oxygen

on phosphorus on phosphorus Addition
Elimination Elimination
Deprotonation Deprotonation

Index Index
112 113
7*S5 P2O5
7OVZWOVY\Z7LU[HJOSVYPKL Phosphus pentoxide
:KDWLW·VXVHGIRU3KRVSKRUXVSHQWDFKORULGHZLOOFRQYHUWDOFRKROVWRDON\OFKOR- Also known as:3KRVSKRULFDQK\GULGHSKRVSKRUXV 9 R[LGH34+

ULGHVDQGFDUER[\OLFDFLGVWRDFLGFKORULGHV DF\OFKORULGHV
:KDWLW·VXVHGIRU32LVDUHDJHQWXVHGIRUGHK\GUDWLRQ,WLVXVHGIRUFRQYHUVLRQ
Similar to:62&O3&O3 RIFDUER[\OLFDFLGVWRDQK\GULGHVDQGDOVRWKHIRUPDWLRQRIQLWULOHVIURPDPLGHV
Example 1: Formation of alkyl bromides from alcohols Similar to:342 WKLVEHKDYHVH[DFWO\WKHVDPHDV32

Example 1: Conversion of carboxylic acids to anhydrides
Example 2: Conversion of amides to nitriles

Example 2: Formation of acid bromides from carboxylic acids
How it works: Conversion of carboxylic acids to anhydrides
How it works: Formation of alkyl chlorides and acyl chlorides

Carboxylic
Proton transfer acid #2
3&ORSHUDWHVE\DPHFKDQLVPHVVHQWLDOO\LGHQWLFDOWRWKDWRI3&O3DQG3%U3
Carboxylic acid #1
Deprotonation Elimination
Anhydride
How it works: Conversion of amides to nitriles
Proton transfer
Addition
Elimination
Amide
Deprotonation

Index
Nitrile
http://masterorganicchemistry.com Index
Index Index
114 115
Pd/C Pt
7HSSHKP\TVUJHYIVU 7SH[PU\T
:KDWLW·VXVHGIRU3DOODGLXPDGVRUEHGRQFKDUFRDO FDUERQ >3G&@LVDKHW- Also known as:3W&

HURJHQHRXVFDWDO\VW,QWKHSUHVHQFHRIK\GURJHQJDV + LWZLOOFRQYHUWDONHQHV
DQGDON\QHVWRDONDQHVZLWKsynDGGLWLRQRIK\GURJHQ :KDWLW·VXVHGIRU3ODWLQXPD´QREOHPHWDOµLVXVHGIRUWKHUHGXFWLRQRIFDUERQ
FDUERQPXOWLSOHERQGVLQWKHSUHVHQFHRIK\GURJHQJDV
Similar to:/LQGODU·VFDWDO\VW´SDOODGLXPµ 3G SODWLQXP 3W SODWLQXPRQFDUERQ Similar to:3DOODGLXPRQFDUERQ 3G& 1LFNHO 1L 5XWKHQLXPRQFDUERQ 5X&
3W& QLFNHO 1L UXWKHQLXPRQFDUERQ 5X& UKRGLXPRQFDUERQ 5K
([DPSOH5HGXFWLRQFRQYHUVLRQRIDONHQHVWRDONDQHV
([DPSOH5HGXFWLRQFRQYHUVLRQRIDONHQHVWRDONDQHV
([DPSOH5HGXFWLRQFRQYHUVLRQRIDON\QHVWRDONDQHV ([DPSOH5HGXFWLRQFRQYHUVLRQRIDON\QHVWRDONDQHV
([DPSOH5HGXFWLRQFRQYHUVLRQRIQLWURJURXSVWRSULPDU\DPLQHV ([DPSOH5HGXFWLRQFRQYHUVLRQRIDUHQHVWRF\FOLFDONDQHV
([DPSOH5HGXFWLRQFRQYHUVLRQRIQLWULOHVWRSULPDU\DPLQHV
How it works: Hydrogenation

/LNHSDOODGLXPRQFDUERQ 3G& SODWLQXPLVDKHWHURJHQHRXVFDWDO\VW%RWK
([DPSOH5HGXFWLRQFRQYHUVLRQRILPLQHVWRDPLQHV K\GURJHQJDVDQGWKHDONHQHDUHDGVRUEHGRQWRWKHVXUIDFHRIWKHFDWDO\VW
7KHK\GURJHQVDUHWKHQGHOLYHUHGLQsynIDVKLRQ
([DPSOH5HGXFWLRQFRQYHUVLRQRIDUHQHVWRF\FOLFDONDQHV
How it works: Hydrogenation

%RWKK\GURJHQJDVDQGWKHDONHQHDUHDGVRUEHGRQWRWKHVXUIDFHRIWKHFDWDO\VW
7KHK\GURJHQVDUHWKHQGHOLYHUHGLQsynIDVKLRQ$GVRUELQJSDOODGLXPRQWRD
PDWHULDOOLNHFKDUFRDO & DOORZVIRUDKLJKVXUIDFHDUHD

e
Index Index
116 117
PCC 76*S3
7`YPKPUP\TJOSVYVJOYVTH[L 7OVZWOVY\ZV_`JOSVYPKL
:KDWLW·VXVHGIRU3\ULGLQLXPFKORURFKURPDWH 3&& LVDUHDJHQWIRUWKH :KDWLW·VXVHGIRU3KRVSKRUXVR[\FKORULGH 32&O3 LVXVHGIRUWKHGHK\GUDWLRQ

R[LGDWLRQRISULPDU\DOFRKROVWRDOGHK\GHVDQGVHFRQGDU\DOFRKROVWRNHWRQHV RIDOFRKROVWRDONHQHV(VVHQWLDOO\LWFRQYHUWVDOFRKROVWRDJRRGOHDYLQJJURXS
,WLVPXFKPLOGHUWKDQUHDFWDQWVVXFKDV+&U24DQG.0Q2 ZKLFKZLOOR[LGL]H ZKLFKLVWKHQUHPRYHGE\DGGHGEDVH RIWHQS\ULGLQH ,WFDQDOVREHXVHGWR
SULPDU\DOFRKROVWRFDUER[\OLFDFLGV FRQYHUWDPLGHVWRQLWULOHV
Similar to:&U23S\ULGLQH'HVV0DUWLQSHULRGLQDQH '03
Similar to:/L$O+4 /$+ /L$O+ 2W%X
([DPSOH2[LGDWLRQFRQYHUVLRQRISULPDU\DOFRKROVWRDOGHK\GHV
3
([DPSOH(OLPLQDWLRQFRQYHUVLRQRIDOFRKROVWRDONHQHV
([DPSOH2[LGDWLRQFRQYHUVLRQRIVHFRQGDU\DOFRKROVWRNHWRQHV
How it works: Oxidation of primary alcohols to aldehydes Example 2: Conversion of amides to nitriles
7KHDOFRKROFRRUGLQDWHVWRWKHFKURPLXP 9, DWRPGLVSODFLQJFKORULQHZKLFKWKHQ
DFWVDVDEDVHUHVXOWLQJLQIRUPDWLRQRIDQHZ&²2ERQGDQGUHGXFWLRQRI&U 9, WR
&U ,9
How it works: Elimination of alcohols to alkenes

,QWKLVUHDFWLRQWKHDOFRKROR[\JHQDWWDFNVSKRVSKRUXVGLVSODFLQJFKORULGHLRQ
Addition
7KHQFOLPLQDWLRQRIWKHQHZO\IRUPHGOHDYLQJJURXSOHDGVWRIRUPDWLRQRIWKH
DONHQH
Proton transfer
Loss of chloride
Elimination Attack of oxygen on
of Cl phosphorus
Use of pyridine as a base

Elimination: Elimination
here will speed up the
formation of C3O
reaction considerably.
bond
Pyridinium chloride
(byproduct)

Index Index
118 119
PPh3 Pyridine
;YPWOLU`SWOVZWOPUL
Also known as:7ULSKHQ\OSKRVSKDQH Also known as:2IWHQDEEUHYLDWHG´S\UµRU´S\µ

:KDWLW·VXVHGIRU3\ULGLQHLVDPLOGEDVH6LQFHLWEHDUVQRFKDUJHLWLVHVSH-
:KDWLW·VXVHGIRU33K3LVFRPPRQO\XVHGIRUIRUPDWLRQRI\OLGHVLQWKH:LWWLJ FLDOO\VROXEOHLQRUJDQLFVROYHQWV,WLVRIWHQXVHGLQUHDFWLRQVWKDWJHQHUDWH+&O
UHDFWLRQ,WFDQDOVREHXVHGIRUUHGXFWLYHZRUNXSLQWKHR]RQRO\VLVRIDONHQHV DQGRWKHUVWURQJDFLGVLWDFWVPXFKOLNHD´VSRQJHµIRUVWURQJDFLG
Similar to:'LPHWK\OVXOÀGH LQWKHUHGXFWLYHZRUNXSRIR]RQRO\VLV Similar to:7ULHWK\ODPLQH 1(W3 1D2+RWKHUEDVHV
([DPSOH:LWWLJUHDFWLRQFRQYHUVLRQRIDOGHK\GHVNHWRQHVWRDONHQHV
Example 1: Conversion of alcohols to tosylates or mesylates
Pyridine acts as a
weak base in this
reaction, neutralizing
the HCl generated
here.
How it works: The Wittig reaction How it works: Formation of tosylates/mesylates

7ULSKHQ\OSKRVSKLQHLVDJRRGQXFOHRSKLOHDQGZLOOUHDFWZLWKDON\OKDOLGHVWR
IRUPSKRVSKRQLXPVDOWV7UHDWPHQWRIWKHSKRVSKRQLXPVDOWZLWKDVWURQJEDVH
VXFKDVn%X/LUHVXOWVLQWKHIRUPDWLRQRIDQ\OLGH5HDFWLRQRIWKH\OLGHZLWKDQ
DOGHK\GHRUNHWRQHJLYHVDQR[DSKRVSKDWDQHZKLFKRSHQVWRJLYHDQDONHQH
DQGWULSKHQ\OSKRVSKLQHR[LGH
Deprotonation
SN2 with strong base
Phosphonium salt Note that the role of pyridine

here is simply to act as a base,
removing the HCl generated
during this reaction.
<oxaphosphatane= <Pyridinium chloride=

Ylide
Driving force for this
Breakdown of the oxaphosphatane gives
reaction is formation of
an alkene and triphenylphosphine oxide
the strong P=O bond
this is <triphenylphosphine oxide=

Index Index
120 121
9H¶5P ROÐOR
9HUL`5PJRLS Peroxides
:KDWLW·VXVHGIRU5DQH\QLFNHOLVDUHDJHQWIRUWKHUHGXFWLRQ K\GURJHQDWLRQ RI :KDWLW·VXVHGIRU3HUR[LGHVDUHXVHGWRLQLWLDWHIUHHUDGLFDOUHDFWLRQV7KH

GRXEOHERQGV,WLVDOVRXVHGIRUWKHGLUHFWUHSODFHPHQWRIVXOIXUE\K\GURJHQ R[\JHQR[\JHQERQGLVYHU\ZHDNDQGZLOOIUDJPHQWKRPRO\WLFDOO\WRJHQHUDWH
IUHHUDGLFDOV
Similar to:3G&3W1LDQGRWKHUKHWHURJHQHRXVFDWDO\VWV Similar to:$,%1EHQ]R\OSHUR[LGH
([DPSOH)UHHUDGLFDODGGLWLRQFRQYHUVLRQRIDONHQHVWRDON\OEURPLGHV
([DPSOH5HGXFWLRQFRQYHUVLRQRIWKLRDFHWDOVWRDONDQHV
Note that Br adds to the
less substituted carbon
<anti-Markovnikov=
([DPSOH5HGXFWLRQFRQYHUVLRQRIWKLRDFHWDOVWRDONDQHV How it works: Free radical bromination
This example shows the formation 3HUR[LGHVZKLFKKDYHWKHJHQHUDOIRUPXOD52²25ZLOOIUDJPHQWKRPRO\WLFDOO\

of the thioacetal from the ketone XSRQKHDWLQJWRSURYLGHDONR[\UDGLFDOV52
using 1,3-propanedithiol and BF3
7KHVHUDGLFDOVDUHYHU\UHDFWLYHDQGZLOOUHDGLO\UHPRYHK\GURJHQIURPYDULRXV
([DPSOH+\GURJHQDWLRQFRQYHUVLRQRIDONHQHVWRDONDQHV JURXSVOHDGLQJWRIUHHUDGLFDOFKDLQSURFHVVHV
How it works: Reduction of thioacetals $GGLWLRQRFFXUVWRWKHOHVVVXEVWLWXWHGFDUERQ LH´DQWL0DUNRYQLNRYµEHFDXVH

5DQH\1LFNHOLVDQDOOR\RIQLFNHODQGDOXPLQXPZKLFKFRQWDLQVDGVRUEHG WKLVUHVXOWVLQWKHPRUHVWDEOH LHPRVWVXEVWLWXWHG VHFRQGDU\UDGLFDO
K\GURJHQRQLWVVXUIDFH KHQFH+JDVLVQRWQHFHVVDU\LQPDQ\FDVHV ,WV
H[DFWPRGHRIDFWLRQIRUWKHUHGXFWLRQRI&²6ERQGVLVVRPHZKDWREVFXUH
7KHEURPLQHUDGLFDOJHQHUDWHGKHUHFDQ
UHHQWHUWKHUHDFWLRQDWSURSDJDWLRQVWHS
DGGLWLRQWRWKHDONHQH

Index Index
122 123
SO3 SOBr2
:\SM\Y[YPV_PKL ;OPVU`SIYVTPKL
:KDWLW·VXVHGIRU6XOIXUWULR[LGHLVDUHDJHQWIRUWKHVXOIRQ\ODWLRQRIDURPDWLF :KDWLW·VXVHGIRU7KLRQ\OEURPLGHLVDXVHIXOUHDJHQWIRUWKHIRUPDWLRQRIDON\O
JURXSV,QWKHSUHVHQFHRIDFLGLWZLOOOHDGWRWKHIRUPDWLRQRIVXOIRQLFDFLGV EURPLGHVIURPDOFRKROVDVZHOODVDFLGEURPLGHV DF\OEURPLGHV IURPFDUER[\OLF
([DPSOH6XOIRQ\ODWLRQFRQYHUVLRQRIDUHQHVWRDU\OVXOIRQLFDFLGV DFLGV
Similar to:3%U362&O RSHUDWHVE\WKHVDPHPHFKDQLVP
Example 1: Conversion of alcohols to alkyl bromides
How it works: Formation of sulfonic acids

623LVRIWHQXVHGLQWKHSUHVHQFHRIVXOIXULFDFLG3URWRQDWLRQRI623JLYHV
623+DEHWWHUHOHFWURSKLOHWKDQ623
Example 2: Conversion of carboxylic acids to acyl bromides
Often written
HSO43
How it works: Formation of alkyl bromides

7KH623+LVWKHQDWWDFNHG 'HSURWRQDWLRQUHJHQHUDWHV Identical in all respects to SOCl2 (see section)
E\WKHDURPDWLFULQJ DURPDWLFLW\
Note that H2SO4 is regenerated

in this step; it is a catalyst here.
,IWUHDWHGZLWKVWURQJDFLGLQWKHDEVHQFHRI623WKH623+FDQEHUHPRYHG
7KLVPDNHVWKH623+DXVHIXOUHPRYDEOHÉORFNLQJJURXSµ
SO3 is lost as a gas
H2SO4
This allows for formation of the ortho chlorinated

product without any para substituted product
because the SO3H <blocked= the para position

Index Index
124 125
:6*S2 Sn
;OPVU`SJOSVYPKL Tin
:KDWLW·VXVHGIRU7KLRQ\OFKORULGHLVXVHGIRUWKHIRUPDWLRQRIDON\OFKORULGHV :KDWLW·VXVHGIRU7LQLVDUHGXFLQJDJHQW,QWKHSUHVHQFHRIVWURQJDFLGVLW
IURPDOFRKROVDQGDFLGFKORULGHV DF\OFKORULGHV IURPFDUER[\OLFDFLGV ZLOOUHGXFHQLWURJURXSVWRDPLQHV
Similar to:3&O33&O62%U Similar to:7LQ ,, FKORULGH 6Q&O ,URQPHWDO )H =LQF =Q
Example 1: Conversion of alcohols to alkyl chlorides ([DPSOH5HGXFWLRQFRQYHUVLRQRIQLWURJURXSVWRDPLQHV
Example 2: Conversion of carboxylic acids to acyl chlorides +RZLWZRUNVReduction of nitro groups

7KHPHFKDQLVPKDVQRWEHHQGHWHUPLQHGZLWKFHUWDLQW\2IWHQQRWGHSLFWHG
LQWH[WERRNV +HUHLVDSRVVLEOHPHFKDQLVP loss of water
How it works: Formation of alkyl chlorides

7KLVUHDFWLRQSURFHHGVWKURXJKDWWDFNRIR[\JHQRQVXOIXUDQGWKHQ6NDWWDFNRI
FKORULGHLRQRQFDUERQUHVXOWLQJLQLQYHUVLRQRIFRQÀJXUDWLRQ62JDVLVOLEHUDWHG
Sn donates electron pair
How it works: Formation of acyl chlorides

$WWDFNRIR[\JHQDWVXOIXULVIROORZHGE\DGGLWLRQRIFKORULGHLRQDQGHOLPLQDWLRQRI
2²62&OZKLFKORVHV&O²WREHFRPH627KHSURGXFWLVDQDF\OFKORULGH
Addition of Sn donates electron

chloride Hydroxylamine
Attack at Elimination of pair to N=O (nitroso)
sulfur chloride
loss of water
Acyl chloride
Sn donates electron pair Amine
Elimination of
@bohring_bot
Deprotonation
oxygen
I
Index Index
128 129
;Z*S TsOH
p;VS\LULZ\SMVU`SJOSVYPKL
as p;VS\LULZ\SMVUPJHJPK
Also known as:7RV&OS7V&O7RV\OFKRULGH Also known as:7RVLFDFLG7RV2+

:KDWLW·VXVHGIRU7RV\OFKORULGH 7V&O ZLOOFRQYHUWDOFRKROVWRVXOIRQDWHVZKLFK :KDWLW·VXVHGIRU7RVLFDFLGLVDVWURQJDFLGVLPLODULQVWUHQJWKWRVXOIXULFDFLG
DUHH[FHOOHQWOHDYLQJJURXSVLQHOLPLQDWLRQDQGVXEVWLWXWLRQUHDFWLRQV7V2²LVWKH SNDRI² 2QHIHDWXUHLVWKDWWKHFRQMXJDWHEDVHLVDSRRUQXFOHRSKOHZKLFK
FRQMXJDWHEDVHRIWKHVWURQJDFLG7V2+ PDNHVLWXVHIXOIRUWKHGHK\GUDWLRQRIDOFRKROVWRIRUPDONHQHV$OVRLWLVDZKLWH
Similar to:0HV\OFKORULGH 0V&O SEURPREHQ]HQHVXOIRQ\OFKORULGH %V&O FU\VWDOOLQHVROLGZKLFKPDNHVLWVOLJKWO\PRUHFRQYHQLHQWWRXVHWKDQ+624LQ
Example 1: Conversion of alcohols to alkyl tosylates VRPHFDVHV
Similar to:6XOIXULFDFLG +624
([DPSOH(OLPLQDWLRQFRQYHUVLRQRIDOFRKROVWRDONHQHV
How it works: Acid-catalyzed elimination of alcohols to give alkenes
Example 2: Substitution of tosylates

Formation of
a carbocation
Example 3: Elimination of tosylates
Protonation makes OH a better Deprotonation to

leaving group form an alkene
How it works: Tosylates as leaving groups
:HDNEDVHVDUHH[FHOOHQWOHDYLQJJURXSV%\FRQYHUWLQJ2+ DVWURQJEDVHDQG
SRRUOHDYLQJJURXS WR27V DPXFKZHDNHUEDVHDQGOHDYLQJJURXS LWEHFRPHV
PDQ\RUGHUVRIPDJQLWXGHHDVLHUWRGRVXEVWLWXWLRQDQGHOLPLQDWLRQUHDFWLRQV
Note how the negative charge on oxygen can be delocalized

on to the other oxygen atoms through resonance.
Note that TsOH is regenerated here

(it is a catalyst in this reaction)

Index Index
130 131
Zn Zn/Cu
Zinc APUJ*VWWLY*V\WSL
:KDWLW·VXVHGIRU=LQFLVDPHWDOUHGXFLQJDJHQW,WLVXVHIXOIRUWKHUHGXFWLRQRI :KDWLW·VXVHGIRU=LQFFRSSHUFRXSOHLVDUHGXFLQJDJHQWXVHGWRIRUP
R]RQLGHVDQGDOVRLQWKHUHGXFWLRQRIQLWURJURXSVWRDPLQHV LQWKHSUHVHQFHRI FDUEHQHV DFWXDOO\´FDUEHQRLGVµ IURPDON\OGLKDOLGHV:KHQWKHVHDUH
DFLG DGGHGWRDONHQHVWKH\IRUPF\FORSURSDQHV
Similar to:'LPHWK\OVXOÀGH LQZRUNXSRIR]RQRO\VLV 6Q LQUHGXFWLRQRIQLWUR
JURXSV ([DPSOH6LPPRQV6PLWKUHDFWLRQIRUPDWLRQRIF\FORSURSDQHVIURP
alkenes
([DPSOH2]RQRO\VLV UHGXFWLYHZRUNXS FRQYHUVLRQRIDONHQHVWR
aldehydes/ketones
([DPSOH5HGXFWLRQFRQYHUVLRQRIQLWURJURXSVWRSULPDU\DPLQHV
How it works: Cyclopropanation of alkenes
=LQFFRSSHUFRXSOHLVDQDOOR\RI]LQFDQGFRSSHUWKDWFDQUHGXFHGLKD-
OLGHVWRPHWDOFDUEHQRLGV7KHFDUEHQRLGSHUIRUPVWKHF\FORSURSDQDWLRQ
How it works: Reduction of ozonides UHDFWLRQ
=LQFLVHDVLO\R[LGL]HGDQGFDQGRQDWHHOHFWURQVWRYDULRXVJURXSV2QH
DSSOLFDWLRQLVLQWKHUHGXFWLRQRIR]RQLGHV
=LQFFRSSHUFRXSOHLWVHOILVDPHWDOFOXVWHU QRWDPROHFXOH 7KHPHFKD-

QLVPRIDFWLRQIRUIRUPDWLRQRIWKH=QFDUERQERQGLVSUREDEO\VLPLODUWR
WKDWRIRUJDQROLWKLXPDQG*ULJQDUGUHDJHQWV
Ozonide
)RUDVXJJHVWLRQRQKRZPHWDOVVXFKDV=Q6QDQG)HUHGXFHQLWUR
JURXSVLQWKHSUHVHQFHRIDFLGVVXFKDV+&OVHHWKHVHFWLRQRQWLQ 6Q

Index Index
132 133
Odds And Ends
APUJHTHSNHT
'%8 'LD]DELF\FORXQGHFHQH
%DVHXVHGLQHOLPLQDWLRQUHDFWLRQV%XON\QRQQXFOHRSKLOLF
EDVH
:KDWLW·VXVHGIRU,QWKHSUHVHQFHRIDFLG]LQFDPDOJDPZLOOUHGXFHNHWRQHVWR
DONDQHVLQDSURFHVVFDOOHGWKH&OHPPHQVHQUHDFWLRQ RU&OHPPHQVHQUHGXFWLRQ Ethylene glycol
8VHGDVVROYHQWLQ:ROII.LVKQHUDQGDVDSURWHFWLQJJURXS
DFHWDO IRUNHWRQHV+LJKERLOLQJVROYHQW
Example 1: The Clemmensen Reduction
Note: these reactions tend to KHSO3 3RWDVVLXPELVXOIDWH 8VHGLQGLK\GUR[\ODWLRQUHDFWLRQZRUNXS

work best on ketones adjacent EUHDNVXS´RVPDWHHVWHUµ
to aromatic rings.
How it works: The Clemmensen Reduction 102 1PHWK\OPRUSKROLQH1R[LGH

0HWDOVWKDWDUHIXVHGZLWKPHUFXU\DUHFDOOHGamalgamsDQGWKHLUSUHFLVH
8VHGDVR[LGDQWLQGLK\GUR[\ODWLRQUHDFWLRQRIDONHQHV
PRGHRIDFWLRQLVVRPHZKDWREVFXUH7KHVWURQJDFLG +&O VHUYHVWRDFWLYDWH
$OORZVIRUFDWDO\WLFXVHRI H[SHQVLYH 2V24
WKHFDUERQ\OWRZDUGUHGXFWLRQDVZHOODVDVVLVWLQWKHHYHQWXDOUHPRYDORIWKH
FDUERQ\OR[\JHQDV+2
Oxalyl chloride
6LPODUWRWKLRQ\OFKORULGHXVHGLQ6ZHUQR[LGDWLRQRIDO-
FRKROVWRJLYHDOGHK\GHVDQGNHWRQHV&RQYHUWV'062
WRDFWLYHHOHFWURSKLOH
See a reagent in your introductory course or textbook

WKDWLVQ·WGHSLFWHGDQ\ZKHUHLQWKH*XLGH"
Click To Leave Feedback

Index Index
134 135
*VTTVU(IIYL]PH[PVUZHUK;LYTZ -\UJ[PVUHS.YV\WZ
Methyl Ac acetyl
Me
Et Ethyl
Ts
Pr Propyl
Bu Butyl p-toluenesulfonyl
(tosyl)
i3U isopropyl Ms methanesulfonyl

(mesyl)
s%X sec-butyl Bs
i%X isobutyl
p-bromobenzenesulfonyl
(brosyl)
t%X tert-butyl
Allyl
phenyl 9LQ\O
3K &6H5Ð)
Propargyl
%Q &6H5CH2Ð) benzyl

Piv Pivaolyl

Index Index
136 137
W2HZVM*VTTVU-\UJ[PVUHS.YV\WZ W2HZVM*VTTVU-\UJ[PVUHS.YV\WZ

Index Index
138 139
5V[LZVU(JPKZ 5V[LZVU(JPKZ

Index Index
140 141
5V[LZVU)HZLZ 6_PKPaPUN(NLU[Z

Index Index
142 143
6_PKPaPUN(NLU[Z Reducing Agents

Index Index
144 145
Reducing Agents 6YNHUVTL[HSSPJ9LHNLU[Z

Index Index
146 147
6YNHUVTL[HSSPJ9LHNLU[Z 9LHNLU[ZMVY4HRPUN(SR`S
(J`S/HSPKLZ

Index Index
148 149
9LHNLU[Z0U]VS]PUN(YVTH[PJ9PUNZ r 9LHNLU[Z0U]VS]PUN(YVTH[PJ9PUNZ

Index Index
150 151
Types of Arrows ;`WLZVM:VS]LU[Z

Index Index
152 Reagent 153
Protecting Groups
.Y\IIZ»*H[HS`Z[
1RWH&\ F\FORKH[DQHVR3&\3LV
Protection of alcohols
WULF\FORKH[\OSKRVSKLQH
Deprotection: TBAF or
aqueous acid :KDWLW·VXVHGIRU5HDJHQWXVHGIRUROHÀQPHWDWKHVLV7KUHHPDLQUHDFWLRQV
DUHHQFRXQWHUHGZKLFKDOOIROORZWKHVDPHW\SHRIPHFKDQLVPULQJFORVLQJPH-
Silyl ether WDWKHVLVFURVVPHWDWKHVLVDQGULQJRSHQLQJPHWDWKHVLVSRO\PHUL]DWLRQ
Deprotection: aqueous Example 1: Ring closing metathesis

acid
Acetal
Example 2: Cross metathesis

Deprotection: aqueous
acid or base The squiggly line indicates a mixture of
Ester cis and trans isomers
Protection of aldehydes and ketones
([DPSOH5LQJRSHQLQJPHWDWKHVLVSRO\PHUL]DWLRQ
acid
Acetal In practice, only works
well for strained alkenes
(like norbornene)
<norbornene=
acid
Acetal (cyclic)

Index Index
154 *UXEEV·&DWDO\VW 155
How it works: 2OHÀQPHWDWKHVLV *YVZZ*V\WSPUN9LHNLU[Z
(GLWRULDO7KLVUHDJHQWUHDOO\GRHVQ·WEHORQJLQRILQWURGXFWRU\RUJDQLFFKHP-
LVWU\FRXUVHVEHFDXVHWKHNH\UHDFWLRQVRIWUDQVLWLRQPHWDOV OLJDQGH[FKDQJH Alkenyl halide:$OOSDOODGLXPFDWDO\]HGUHDFWLRQVFRYHUHGLQLQWURGXFWRU\FRXUVHV
FRRUGLQDWLRQR[LGDWLYHDGGLWLRQUHGXFWLYHHOLPLQDWLRQ KDYHQRWEHHQSURSHUO\ KDYHDQDONHQ\O RUDU\O KDOLGHFRXSOLQJSDUWQHU7KHÀUVWVWHSRIFURVVFRXSOLQJ
LQWURGXFHG,QWURGXFLQJWUDQVLWLRQPHWDOUHDFWLRQVMXVWFDXVHVPRUHFRQIXVLRQ UHDFWLRQV LQFOXGLQJWKH+HFN LVR[LGDWLYHDGGLWLRQRI3G LQWRWKH&;ERQG
5SJnBUFT
)RURXUPHFKDQLVPZH·OOVLPSOLI\GUDZLQJE\UHSUHVHQWLQJUXWKHQLXP also
DQGWKHDWWDFKHGFKORULQHVDQGSKRVSKLQHVDV´0µ work
Coupling partner:7KHGLIIHUHQFHVLQ´QDPHVµDPRQJWKHGLIIHUHQWSDOODGLXPFDW-
DO\]HG&&ERQGIRUPLQJUHDFWLRQVERLOVGRZQWRWKHFKRLFHRIFRXSOLQJSDUWQHU
equals
,QWKH+HFNUHDFWLRQWKHFRXSOLQJSDUWQHULVDQDONHQH,QWKH6X]XNLUHDFWLRQ
WKHFRXSOLQJSDUWQHULVDERURQLFDFLGRUERURQLFHVWHU,QWKH6WLOOHUHDFWLRQWKH
7KH*UXEEVFDWDO\VWFRPHVDWWDFKHGWRSKHQ\OEXWWKHDFWLYHFDWDO\VWLVJHQ- FRXSOLQJSDUWQHULVDQRUJDQRVWDQQDQH
HUDOO\UXWKHQLXPPHWK\OLGHQH &+ 5HDFWLRQZLWKRQHHTXLYDOHQWRIDONHQH
WKURXJKWKHJHQHUDOPHFKDQLVPEHORZ UHVXOWVLQWKHDFWLYHFDWDO\VW
Alkene Boronic acid Boronic ester Organostannane
Palladium sources:7KHPRVWFRPPRQO\REVHUYHGVRXUFHRISDOODGLXPLV
+HUH·VWKHFDWDO\WLFF\FOHIRUDW\SLFDOULQJFORVLQJPHWKDWKHVLV7KH 3G 33K3 4´WHWUDNLVµEHFDXVHLWLVDVRXUFHRI3GLQWKH R[LGDWLRQVWDWH$QRWKHU
FXUYHGOLQHUHSUHVHQWVDFDUERQFKDLQRILQGHWHUPLQDWHOHQJWK VRXUFHRI3G LV3G GED 3ZKHUH´GEDµLVGLEHQ]\OLGHQHDFHWRQH$ÀQDOVRXUFH
RI3GLV3G 2$F 7KLVLVJHQHUDOO\FRQYHUWHGWR3G XQGHUWKHUHDFWLRQFRQGL-
Alkene WLRQV
metathesis )RURXUSXUSRVHVWKHUHLVQRSUDFWLFDOGLIIHUHQFHEHWZHHQWKHVHUHDJHQWV
product Coordination to
alkene
Catalyst
resting
state
Pd(PPh3)4 Pd2(dba)3 Pd(OAc)2
LIgands:´/LJDQGVµDUH/HZLVEDVHVWKDWFRRUGLQDWHWRPHWDOVIRUH[DPSOHWULSK-
Reverse HQ\OSKRVSKLQH33K36RPHYDULDQWVRQWULSKHQ\OSKRVSKLQHDUHVRPHWLPHVVHHQ
cycloaddition IRUH[DPSOHWULF\FORKH[\OSKRVSKLQH 3&\3 RUWULRWRO\OSKRVSKLQH
#2 )RURXUSXUSRVHVWKHUHLVQRSUDFWLFDOGLIIHUHQFHEHWZHHQWKHVHUHDJHQWV
Cycloaddition Cycloaddition
#2
Triphenyl phosphine Tricyclohexyl Tri o-tolyl phosphine

(PPh3) phosphine (PCy3)
Coordination to
Reverse cycloaddition (forming
second alkene Additives:8VHGWRKHOSWKHUHDFWLRQSURFHHGLQVRPHZD\7KHVHDUHXVXDOO\
@bohring_bot
ethylene byproduct)
EDVHVVXFKDV1(WLQWKH+HFNUHDFWLRQRU1D2+LQWKH6X]XNLUHDFWLRQ
Index Index
156 157
*YVZZ*V\WSPUN *YVZZ*V\WSPUN
How it works: Heck reaction How it works: Suzuki reaction
Using NEt3 as a
base <mops up= the
HBr that forms
This step tends to

put Pd on the least
substituted carbon
(sterics)
7KHEHWDK\GULGHHOLPLQDWLRQVWHSUHTXLUHVWKH3GWREH´V\QµZLWKWKH
K\GURJHQ)RUPDWLRQRIWUDQVDONHQHVLVSUHIHUUHG


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The

([DPSOH6XEVWLWXWLRQ 6N1) conversion of alkyl halides to ethers

Example 2: Conversion of carboxylic acids to anhydrides ([DPSOH7ROOHQVR[LGDWLRQFRQYHUVLRQRIDOGHK\GHVWRFDUER[\OLFDFLGV

How it works: SN1 Reaction of alkyl halides

Activation of Ac2O Acylium ion

Attack of aromatic ring on Re-aromatization (often shown

Similar to: $J123 Similar to: 52²25 ´SHUR[LGHVµ EHQ]R\OSHUR[LGH

How it works: Free-radical halogenation of alkenes

Organic Chemistry Reagent Guide @bohring_bot

Also known as:$OXPLQXPWULEURPLGH Also known as:$OXPLQXPWULFKORULGH

How it works: Friedel-Crafts acylation

Organic Chemistry Reagent Guide @bohring_bot

How it works: Meerwein-Ponndorf-Verley Oxidation :KDWLW·VXVHGIRU%RURQWULÁXRULGHLVDVWURQJ/HZLVDFLG,WLVFRPPRQO\XVHG

How it works: Formation of thioacetals

The aluminum alkoxide can go on to

Organic Chemistry Reagent Guide @bohring_bot

How it works: Hydroboration of alkenes How it works: Hydroboration of alkynes

Organic Chemistry Reagent Guide @bohring_bot

How it works: Bromination of alkenes

Example 3: Conversion of alkenes to halohydrins

Example 7: Conversion of enolates to _EURPRNHWRQHV

Organic Chemistry Reagent Guide @bohring_bot

How it works: Bromination of enolates

How it works: Halogenation of alkanes

Organic Chemistry Reagent Guide @bohring_bot

:KDWLW·VXVHGIRU&KORULQHLVDYHU\JRRGHOHFWURSKLOH,WZLOOUHDFWZLWKGRXEOH Example 8: The haloform reaction

Example 2: Conversion of alkenes to chlorohydrins

In a nucleophilic solvent such as H2O, water will attack the

Example 6: Conversion ot enolates to _FKORURNHWRQHV

How it works: Chlorination of ketones under acidic conditions

Organic Chemistry Reagent Guide @bohring_bot

How it works: Chlorination of enolates :KDWLW·VXVHGIRU&\DQLGHLRQLVDJRRGQXFOHRSKLOH,WFDQEHXVHGIRUVXEVWL-

Same as: .&11D&1/L&1

How it works: Nucleophilic substitution

Cyanide ion is a good

How it works: Benzoin condensation

Organic Chemistry Reagent Guide @bohring_bot

:KDWLW·VXVHGIRU&U23LVDQR[LGDQW:KHQS\ULGLQHLVSUHVHQWLWLVDPLOGR[- How it works: Oxidation of primary alcohols to carboxylic acids

After proton transfer Second deprotonation results in

Example 3: Oxidation of primary alcohols to carboxylic acids

How it works: Oxidation of primary alcohols to aldehydes

Organic Chemistry Reagent Guide @bohring_bot

Also known as:&XSURXVEURPLGH Also known as:&XSURXVFKORULGH

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The radical then abstracts Br The radical then abstracts Cl

Organic Chemistry Reagent Guide @bohring_bot

How it works: Formation of organocuprates

How it works: Formation of amides from carboxylic acids and amines

This byproduct is called a <urea=

Organic Chemistry Reagent Guide @bohring_bot

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Example 2: Cyclopropanation of alkenes

How it works: Reductive workup for ozonolysis

How it works: Formation of methyl esters

How it works: Wolff Rearrangement

Organic Chemistry Reagent Guide @bohring_bot

Example 1: Deuterium reagents as acids Example 1: Reduction of esters to aldehydes

Example 2: Reduction of ketones to secondary alcohols

Example 2: Hydroboration of alkenes

Example 3: Reduction of aldehydes to primary alcohols

Example 3: Reduction of ketones

Organic Chemistry Reagent Guide @bohring_bot

How it works: Reduction of esters to aldehydes

Organic Chemistry Reagent Guide @bohring_bot

([DPSOH6XEVWLWXWLRQ 6N1) conversion of alkyl halides to ethers

Example 2: Conversion of carboxylic acids to anhydrides ([DPSOH7ROOHQVR[LGDWLRQFRQYHUVLRQRIDOGHK\GHVWRFDUER[\OLFDFLGV

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How it works: Meerwein-Ponndorf-Verley Oxidation :KDWLW·VXVHGIRU%RURQWULÁXRULGHLVDVWURQJ/HZLVDFLG,WLVFRPPRQO\XVHG

Example 7: Conversion of enolates to _EURPRNHWRQHV

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Example 6: Conversion ot enolates to _FKORURNHWRQHV

How it works: Chlorination of enolates :KDWLW·VXVHGIRU&\DQLGHLRQLVDJRRGQXFOHRSKLOH,WFDQEHXVHGIRUVXEVWL-

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:KDWLW·VXVHGIRU&U23LVDQR[LGDQW:KHQS\ULGLQHLVSUHVHQWLWLVDPLOGR[- How it works: Oxidation of primary alcohols to carboxylic acids

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Also known as:)HUULFEURPLGHLURQWULEURPLGH

Example 1: Reduction: conversion of nitro groups to primary amines ([DPSOH)ULHGHO&UDIWVDF\ODWLRQFRQYHUVLRQRIDUHQHVWRDU\ONHWRQHV

How it works: Reduction of nitro groups ([DPSOH)ULHGHO&UDIWVDON\ODWLRQFRQYHUVLRQRIDUHQHVWRDON\ODUHQHV

How it works: Friedel-Crafts Acylation Also known as:)HUULFFKORULGHLURQWULFKORULGH

Acylium ion ([DPSOH(OHFWURSKLOLFFKORULQDWLRQFRQYHUVLRQRIDUHQHVWRDU\OFKORULGHV

How it works: Addition to epoxides :KDWLW·VXVHGIRU+\GURJHQJDVLVXVHGIRUWKHUHGXFWLRQRIDONHQHVDON\QHV

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:KDWLW·VXVHGIRU+\GUREURPLFDFLGLVDVWURQJDFLG,WFDQDGGWRFRPSRXQGV How it works: Addition to alkynes

:KDWLW·VXVHGIRU+\GURFKORULFDFLGLVDVWURQJDFLG$VDUHDJHQWLWFDQUHDFW How it works: Addition to alkynes

:KDWLW·VXVHGIRU0HUFXULFDFHWDWHLVDXVHIXOUHDJHQWIRUWKHR[\PHUFXUDWLRQ How it works: Oxymercuration of alkynes

([DPSOH2[\PHUFXUDWLRQFRQYHUVLRQRIDON\QHVWRNHWRQHV Tautomerization favors the

How it works: Addition to alkynes :KDWLW·VXVHGIRU3HULRGLFDFLGLVDVWURQJR[LGL]LQJDJHQW,WLVPRVWFRPPRQO\

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:KDWLW·VXVHGIRU+\GURJHQSHUR[LGHLVXVHGDVDQR[LGDQWLQWKHK\GURERUDWLRQ How it works: Oxidative workup for ozonolysis

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:KDWLW·VXVHGIRU,RGLQHLVDQH[FHOOHQWHOHFWURSKLOHGXHWRWKHZHDN,²,ERQG How it works: Iodination of ketones

Example 3: Conversion of ketones to _LRGRNHWRQHV

:KDWLW·VXVHGIRU7KLVVWURQJR[LGL]LQJDJHQWZLOOR[LGL]HSULPDU\DOFRKROV DQG How it works: Oxidation of primary and secondary alcohols

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How it works: Dihydroxylation of alkenes Also known as:.2& &+3 3SRWDVVLXPWHUWEXWR[LGH

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