Alkenes Alkynes

H X
Strong base
R HX Alkene formation R'
Strong base Alkyne formation
X via E2 elimination R R'
R R via double E2

X X X X
HX H Markovnikov xs HX H
R R R R
H X XH
HBr Br Anti-Markovnikov xs X2
X
R R
peroxides
OH OH X
Hg2+/ H2SO4 O
H2O
H Markovnikov
cat. H+ R H2O R R Tautomers
OH
1) Hg(OAc)2/H2O 1) R2BH H
H Markovnikov OH R
2) NaBH4 R (no rearrangement) 2) H2O2/NaOH R
O
H H2
1) R2BH R'
R R' R
OH Anti-Markovnikov cat. Pd/C
2) H2O2/NaOH R OH
1) O3 O R'
X
X2
X 2) H2O R O OH
R
OH H2
X2 R
Halohydrin cis alkene
X Lindlar's Cat.
H2O R R'
base Na0
O R' trans alkene
mCPBA R
NH3 (l)
R Epoxides
H
H2 O
H O
R Nu Nu
cat. Pd/C R
OH R basic Nu
R' cat. OsO4 R'
R R
() Syn-diol Nu OH
H2O2 R
OH acidic OH
1) O3 H O R'
O NaOH R
R' () Anti-diol
R'
2) reduction R O R H2O
H OH
 Alcohols Carbonyl Addition Rxns

oxidation O oxidation O O
HCN HO CN
R OH Cyanohydrin
reduction R H reduction R OH R R' R R'
cat. CN
O
R'=alkyl, H
Na2Cr2O7 R'' O
R''Li
R OH
H2SO4 R OH or R'MgX R R'
OH R''
O C-C
Na2Cr2O7
R'' O
Bond
R R' H2SO4 R R' Forming
O
R R'
PCC
R OH R H
R''

PBr3 R'' PPh3 Wittig Rxn

R OH R Br
R R'

SOCl2 R''OH R''O OH R''OH R''O OR''

R OH R Cl
Acetal/Ketal
cat. H R R' cat. H R R'
OH H2O
R' H2SO4 R'
R
Zaitsev's Rule
R LiAlH4 (LAH) H O

O or NaBH4
TsCl R R'
R OH R O S Tosylate
base R''
O N
R''NH2 Imine
Nu LAH
cat. H R R'
R Nu R H
R'' R'' O
R''2NH N 1) R'''X
NaH R'X Williamson 2) H3O+ R R'''
R OH R O Na cat. H R'
R OR' Etherification R R'
+ R''2NH
Enamine
 Carboxylic Acid Derivatives

O LAH O
O O
OH
R OH R'OH H or OH
R OH R OR' R C N
O R O R NH2
Carboxylic R'OH Esters O Nitriles
Acids R''OH
H or
R OR' R'OH
cat. H cat. H R OR'' OH
1) DIBAL
O O
SOCl2 LAH 2) H3O+
R OH O
R Cl R OH
O
1) 2 RLi NaBH4 R H
2) H3O+ R R'
No Rxn
O
O 1) R'MgX
O R C N
R'NH2 R' 1) DIBAL 2) H3O+ R R'
DCC R N
H 2) H3O+ R H
O O
H2O LAH
O R NH2
R Cl R OH O O
O 1)
Acid Chlorides R'OH OR'' R'OH
R OR''
R OR' 2) H3O+
O
R'NH2 R' R'' O Mechanisms to Review and Know:
2 R''Li
O
R N SN2 (incl. stereochemistry)
H or 2 R''MgX R R''
O O E2 (incl. stereochemistry)
R' OH
SN1 (incl. rearrangements)
R O R'
O O O O E1 (incl. rearrangements)
R'2CuLi
R R' R O R'
R Cl
Additions to alkenes (regiochemistry)
Acetal, imine, and enamine formation
O Fisher esterification, transesterification
Anhydrides So, reactions are
1) DIBAL
similar Electrophilic Aromatic Substitution
2) H3O+ R H
 Important C-C Bond-forming Reactions Conjugate Additions
O O Nu= R2CuLi, RNH2, RSH, CN,
Carbonyl Additions of Enolates
Nu O O
OH O R O
O R
H or OH () (OR)
R (OR) R R
2 R H (OR) (OR) R'
H Nu
O (enolates)
R Aldol 1,4-Addition
R H2O Condensation
H
O Nu O
R Nu
O O Nu= RLi, RMgX, LiAlH4
O R R
R
OH OEt Claisen (OR) (OR)
2 R
OEt Condensation
EtOH
R 1,2-Addition
O O
O O R'X O
R R R''Li R'' O "Normal"
R R R' R R'
or R'MgX
1,2-Addition
R R'
R'= alkyl, H
O O
O O
R'X Ethylacetoacetate
R OEt
Alkene Synthesis
Synthesis
R OEt R''
R' 1) OH O
O Wittig
CO2 2) H O O R'' PPh3 O PPh3 Reaction
R R' R R'
R R OH
R'=alkyl, H
R' R'
O O SN2 with Carbon Nucleophiles
O O
R'X
EtO OEt C N
EtO OEt R C
R' Malonic Ester R X
N
1) OH Synthesis X= halide,
O tosylate R' R
CO2 2) H O O
R'
HO HO OH O
O

R' R'
R'
R' R
 Electrophilic Aromatic Substitution (EAS)

E + BH
E
E
H
B
Sigma Complex

EAS Rxn Electrophile (E ) Reagents Generation of E

Halogenation
X2/FeX3
X Cl or Br (eg. Br2/FeBr3) X3Fe X X

X = Cl, Br
H
Nitration
O O
O N O HNO3/H2SO4 H N
NO2
Nitronium Ion O

Sulfonation O
O
H
O SO3/H2SO4
S O S O
S "fuming sulfuric acid"
SO3H O O O O H
H O
Sulfur Trioxide

Friedel-Crafts
Alkylation R OH2
a) ROH/HA or Lewis Acid

R or R
b) RX/Lewis Acid R X AlX3
R Carbocation or
equivalent c) R R/HA
H A

Friedel-Crafts
Acylation
O O O
R C O R C O + Lewis
R X Acid R X AlX3
R
Acylium Ion
EDG
electron-donating groups (EDG) ortho ortho EWG
= activated ring/ ortho, para directing

electron-withdrawing groups (EWG)

= deactivated ring/ meta directing
meta meta
para