B001

O OH
OH OH2
H -H+ NHMe -H+ +H+
NH2 N Me N Me
+H+ +H+
Me A
CHO OH OH
O H

HO2C
OH
HO2C CO2H CO2H
-H2O -H+ -H2O
MeN O MeN O
N Me +H+ H
B CO2H CO2H
H2O
OH

O
H
CO2H O
-H+ -H+ H -CO
2
MeN OH MeN O MeN OH
+H+ C D
CO2H CO2H CO2H

-H+ -CO2 -H+

MeN O MeN OH MeN O
+H+ H D +H+
O H
O
Cope, A. C: Dryden, H. L.: Howell, C. F Org. Synth., Coll. Vol. Ⅳ 1963, 816
Robinson-Schöpf reaction. A: Formation of a cyclic hemiaminal. B: Mannich reaction C:
Intramolecular Mannich reaction. D: Decarboxylation through the six-membered transition state.

B002
Al(Oi-Pr)3 i-PrO Oi-Pr O
Al -
O O O
Ph Me Me
Me
H
A Me B

Al(Oi-Pr)2
O OH
Ph aq HCl
H

Wilds, A. L. Org. React. 1944, 2.

Meerwein-Ponndorf-Verley reduction. A: Formation of an ate complex. B: H ydride transfer via a six
membered transition state with formation of acetone.

B003
H H
O H O HO NHNH2
+H+ NH2NH2
O O O

H2N H2N
H2O NHNH2 N H N
-H+ -H2O
+H+ O -H+ O O H

N
N H H
-H+ -N2
A B
OH OH
Wharton, P. S.: Bohlen, D. H. J. Org. Chem. 1961, 26, 3615.
Wharton rearrangement. A: Cleavage of the epoxide helped by the nitrogen lone pair of the
hydrazone. B: Elimination of N2 (an extremely good leaving group).

B004

HO
HOO O
-OH-
O
A
O O O

ArSO2NHNH2 O aq K2CO3 O
H B
-H2O N NH N N
SO2Ar SO2Ar

O
O -N2
-ArSO2-

D E
N N
S Ar
O
O
 Reese, C. B.; Sanders, H. P. Synthesis 1981, 276.
Eschenmoser fragmentation. A: Michael addition. B: Formation of an epoxide (the O-O bond is
activated). C: Formation of a hydrazone. D: pKa HCO3- = 10.3, ArSO 2NH2 = 8.5. E: Fragmentation
involving a loss of N2 and a sulfinate ion.

B005

O O OH
H
CN
H CN CN
A B
N CN N N

H
O O O
-CN-
CN CN CN
CN C CN D
N N N

Stetter, H.; Kuhlmann, H.; Lorenz, G. Org. Synth., Coll Vol. Ⅵ 1988, 866
A: Formation of the less favored cyanohydrin carbanion. B: Michael addition. C: Regeneration of the
cyanide ion (cyanohydrin is unstable under basic conditions).

B006
Me Bn
Me Bn N Me Bn
N Cl N
HO S O
HO S H A HO S
NEt3 H H
Me
Me
O
Me O
Me Bn O Me Bn
N N
Me
OH
B HO S HO S H
C O
Me Me
Me O
Me Bn Me Bn
N O
N
HO + Me Me
S D HO S
O O
Me
Stetter, H.; Kuhlmann, H.; Haese, W. Org. Synth., Coll. Vol.Ⅷ 1993. 52
Stetter reaction. A: pKa thiazolinium ion = 10, HNEt3+ = 10.7. B: Generation of a stabilized carbanion
( ref B005). C: Michael addition. D: Regeneration of the thiazolinium ion.
B007

O O O O O O
O O
H OAc
Me O Me O H O O
A B
O
Me

H OAc
O O O
O O
O O O
Me O O Me O Me
C OAc O O AcO O O
O Me Me

O aq HCl O -AcOH O
O O O
D O O O O OH

Me H2O Me

Rajagopalan, S.; Raman, P. V. A. Org. Synth., Coll. Vol. Ⅲ 1955, 425.

Perkin reaction. A: pKa (CH3CO)2O = 13.5, AcOH = 4.8 (a small amount of the acetic anhydride anion
can be formed). B: Intramolecular acyl transfer. C: Formation of a mixed anhydride. D:
Base-catalyzed elimination of acetic acid.

B008
O O MeO H O
HO H Me
Me Me O
A Me B
O O O Me
O

O O O
Me N Me
H -H+
Me
benzene +H+
reflux Me N
O O H
O
 O O O
Me Me Me

HO C
N Me N N
O O O
H
OH

O O O
Me Me HO Me
H

N N N
O OH
H

O O O
Me H Me Me
HCl aq HCl H2O

N N N

O O
-H+ Me -H+ Me

+H+ HO
N O
H

Ramachandran, S.; Newman, M. S. Org. Synth., Coll. Vol. Ⅴ 1973, 486

Robinson annulation. A: pKa RCOCH2COR = 9, H2 O = 15.7. B: Michael addition. C: Formation of
an enamine followed by an intramolecular addition to the ketone.

B009

O O H O

MeO2C OMe MeO2C OMe Ph OMe

A O
H H O
OMe
Ph O OMe

O O
Ph H Ph H Ph H
OMe OMe CO2Me
B O H O O
O
O OMe O
 O O
workup
Ph OMe Ph OMe
C +H+
O
CO2H
OMe
Johnson, W. S.; Daub, G. H. Org. React. 1951. 6
Stobbe condensation. A: pKa CH3CO2R = 24, MeOH = 15.5. B: Formation of a five-membered
lactone. C: Elimination of the carboxylate occurs by avoiding the steric repulsion between the phenyl
and the methoxycarbonyl groups.

B010
Me O Me O
H H3C N N
Ph O H2C N N A Ph O

-N2 Me O

B Ph OMe

Black, T. H. Aldrichimica Acta 1983, 16, 3

A: pKa CH3CO2H = 4.8, CH3N2 = 10.2. B: The SN2 reaction occurs in a solvent cage.

B011
OTs
OTs OTs

O
O O

e e
Li/NH3

OTs
workup
+H+
O O O O
H

Stork, G.; Tsuji, J. J. Am. Chem. Soc. 1961, 83, 2783.

Two successive SET reactions followed by cyclopropane formation.
B012
CN CN CN

H A B
Cl Cl
NH2 H

NH2

CN CN

H NH2

Skorcz, J. A.; Kaminski, F. E. Org. Synth., Coll. Vol. Ⅴ 1973.263

A: pKa CH3CN = 25, NH3 = 35. B: Formation of benzyne followed by an intramolecular nucleophilic
addition.

B013
NaNO2
HCl CuCl
NH2 N N N N
A
e
CuCl2
B

-CuCl Cl
C D
Cl CuCl
Ropp, G. A.; Coyner, E. C. Org. Synth. Coll, Vol.Ⅳ 1963. 27
Meerwein arylation. A: Formation of a diazonium salt ( ref A037). B: SET induces a loss of N2 to form
a phenyl radical. C: Addition of the phenyl radical to butadiene to form a stabilized radical. D:
Recycle of CuCl to continue the radical chain reaction.

B014

H
H CyHN Me
O O S
Cy N C N Cy N C N Cy
A Cy S CyN Me
Me Me Me
O
H Me
 Me
Me
-H + CyHN Me O -Me2S
S Me O
O + Me
+H+ CyHN Me H C
H
B B

or
Me Me
Me
Me O Me O -Me2S
S Me S Me O
C Me
H CH2 H
H H
B

Tidwell, T. T. Org. React. 1990, 39, 297.

Pfitzner-Moffatt o xidation. A: Activation of DCC by protonation. B: Nucleophilic substitution at the
sulfur atom. C: β-Elimination of dimethyl sulfide might proceed either by 1) direct deprotonation with a
base or 2) formation and collapse of a sulfur ylide.

B015

H HO H2O -H2O H

A
Br
H

Br
H
H B Br
Ferreri, C.; Ambrosone, M. Syn. Commun. 1995, 25, 3351.
A: Generation of a carbocation stabilized by a cyclopropyl group. B: Cleavage of the cyclopropane
ring occurs by avoiding the steric repulsion to form the trans-product.

B016
OTs
H H
OTs

H
O O O
H
Ot-Bu
Wharton, P. S.; Hiegel, G. A. J. Org. Chem. 1965, 30, 3254.
Grob fragmentation. This Grob fragmentation can occur when the orbitals of the breaking C-C o-bond
and C-OTs σ-bond overlap on the same plane (antiperiplanar interaction).
B017
Me
AIBN Me Me
n-Bu3SnH n-Bu3Sn I
A

Me Me Me H Me
Me Me
B C
H H

n-Bu3Sn H
Me H Me -n-Bu3Sn Me H Me
Me Me
D
H H H H
Weinges, K.; Reichert, H.; Huber-Patz, U.; Irngartinger, H. Lieb igs Ann. Chem. 1993, 403.
A: Generation of a tin radical ( ref A050). B: Attack on the iodide to initiate the radical chain reaction.
C: 5-exo-trig Radical cyclization. D: 5-exo-dig Radical cyclization.

B018

O O O

Ph O O Ph A Ph O H CCl3 B
CCl3

CCl3 CCl3
-CCl3

C
CCl3
Cl3C H
Dowbenko, R. Org. Synth., Coll Vol. Ⅴ 1973, 93.
A: Homolytic cleavage of dibenzoyl peroxide. B: Generation of a trichloromethyl radical which then
adds to 1,5-cyclooctadiene. C: Transannular radical cyclization.

B019
Ph
Ph Cl -PhCH2Cl
N N O Me N O Me
A B
Cl O Me O Cl O Cl
O Cl
 MeOH -Cl- -H+
N O Me N O Me
reflux C +H+
O Cl O
HOMe
-CO2
N O Me N O NH HCl
D E
O OMe OH
H

Yang, B. V.; O'Rourke, D.; Li, J. Synlett. 1993, 195.

A: Acylation of a tertiary amine. B: Attack of chloride ion on the benzylic position. C: E1 elimination
ofthe chloride followed by addition of methanol, D: Elimination of the carbamic acid helped by the
oxygen lone pair of the methoxy group. E: Decarboxylation.

B020
Me
I Si Me Me
Me Me
Me Si
I
O O O O
Me Me -MeI
C5H11 N C5H11 N
CO2Me A CO2Me B

Me Me
Me Me Me Me
Si Si
O O O O
e
MeOH M OH -Me3SiOMe
C5H11 N C5H11 N
CO2Me C CO2Me

O OH
-CO2 H
C5H11 N C5H11 N
CO2Me CO2Me

Laurent, P.; Braekman, J.-C.; Daloze, D. Eur. J. Org. Chem. 2000, 2057.
A: Sil ylation of the electron-rich oxygen of the carbamate. B: Demethylation by SN2 reaction. C:
Methanolysis of the silyl carbamate.

B021
EtO2C O EtO2C O
PdLn
N O N O PdLn A
 Et
NHEt2 H
EtO2C O EtO2C O N Et
N O Pd N O +
B
Ln LnPd

-PdLn EtO2C
-CO2
NH + NEt2

Genet, J. P.; Blart, E.; Savignac, M.; Lemeune, S.; Lemaire-Audoire, S.; Bernard, J. M.
Synlett 1993, 680.
A: Formation of a π-allylpalladium complex. B: Attack of Et2NH to the π-allylcomplex.

B022
Ph Ph O2N
O O O O
O O N O O N - PhS
S S
N N
A S B
Ph

MeO MeO

PhS H
PhS
B

Ph Ph Ph

O O
S S -SO2
N O H SPh N O NH
H

MeO MeO MeO

Kurosawa, W.; Kan, T.; Fukuyama, T. Org. Synth., Coll. Vol. Ⅹ 2004, 482.
A: Addition of a thiolate ion to the electron deficient aromatic ring to form a Meisenheimer complex. B:
Elimination of an amidosulfurous acid anion which, upon protonation and extrusion of SO2 , gi ves an
amine.

B023
O O
BF3-Et2O
O O BF3
Me Me
Me Me Me Me
 O BF3 O
O CHO
A B Me
Me Me
Me
Me Me
Ryerson, G. D.; Wasson, R. L.; House, H. O. Org. Synth., CoIl Vol.Ⅳ1963, 957.
A: Cleavage of the epoxide to form the more stable tertiary carbecation (formation of a carbocation next
to a carbonyl group is unusually difficult). B: Wagner-Meerwein-type rearrangement.

B024
OH
O Me H
Me S N Me N N OH H2C N N H2C N N
A B
O N O
H OH
OH
O O
O -N2
H2C N N N N
C

de Boer, T. J.; Backer, H. J. Org. Synth., Coll Vol.Ⅳ1963, 225.

A: H ydrolysis of N-methyl-N-nitrososulfonamide. B: Formation of diazomethane. pKa CH3N2 = 10.2,
H2O = 15.7. C: Addition of diazomethane to a ketone followed by ring expansion (cf. Tiffeneau-
Demjanov rearrangement).

B025
Me

NC CN Me NC
Me Me
Me H
Me CN H e
M
Me A B

Kametani, T.; Kondoh, H.; Tsubuki, M.; Honda, T. J. Chem. Soc., Perkin Trans. Ⅰ 1990, 5.
A: 4e Conrotatory electrocyclic reaction to form an o-quinodimethane. B: Intramolecular Diels-Alder
reaction.
B026
FeCl3
FeCl3 FeCl3
O O O

A
SiMe3 SiMe3 SiMe3

O FeCl3 O FeCl3

B C
H SiMe3
SiMe3
X

O FeCl3 O
workup

H H
Jones, T. K.; Denmark, S. E. Helv. Chim. Acta 1983, 66, 2397.
Silicon-directed Nazarov reaction. A: Acti vation of the carbonyl group with FeCl 3, a Lewis acid. B: 4e
Conrotatory electrocyclic reaction. C: Desilylation to form the olefin regioselectively.

B034
hv
3O 1O
2 2
A

1O
O
O 2 O Et3N
O B

O
O O OH
+H+
H
C

Et3N O O

Balci, M. Chem. Rev. 1981, 81, 91.

A: Generation of singlet oxygen. B: Diels-Alder reaction. C: Base-induced cleavage of the
endoperoxide.
B035
hv
3O 1O
2 2
A

O O
1O Ph3P
O 2 O O
O B Ph3P

O
- Ph3P O O

O
PPh3

Balci, M. Chem. Rev. 1981, 81, 91

A: Generation of singlet oxygen. B: Diels-Alder reaction. C: Reductive cleavage of the endoperoxide
with triphenylphosphine. D: Formation of an epoxide via SN2' reaction with elimination of
triphenylphosphine oxide.

B041

CrCl2
Me Br CrCl2 Me
A

Me CrCl2 Ph
Ph Me O
O CrCl2 B
H
H
Ph OCrCl2 OH
workup
Me O
CrCl2 Ph +H+ Ph
H Me Me
Okude, Y.; Hirano, S.; Hi yama, T.; Nozaki, H. J. Am. Chem. Soc. 1977, 99, 3179.
A: Since CrCl2 is a single electron reductant, two molecules of CrCl 2 are needed to convert an alkyl
bromide to the corresponding organochromium species. B: Addition to an aldehyde via a chair-like
six-membered transition state.
B042
O

n-Bu n-Bu
H n-Bu
H
HRh(CO)L2 L2 Rh
A
E CO B

O n-Bu
H n-Bu
L2 Rh H L2 Rh
CO CO
O
D n-Bu CO n-Bu
CO
L2 Rh L2 Rh
CO C CO
H2
Hallman, P. S.; McGarvey, B. R.; Wilkinson, G. J. Chem. Soc. (A) 1968, 3143.
Hydroformylation. A: Complexation of the catalyst with an olefin. B: Hydrometallation. C: Insertion

B045
N N
C
O O S O S
H A B
SCN H H
Ph Ph Ph

N
C
O S Ph S S
H
Ph
H C
Ph O H
C
N
Guss, C. O.; Chamberlain, D. L., Jr. J. Am. Chem. Soc. 1952, 74, 1342.
A: Cleavage of the epoxide by SN2 reaction at the less hindered position. B: Migration of the cyano
group. C: Intramolecular SN2 reaction with inversion of configuration.

B046
Me Me
O HO NMe2 N
-H+ HO
H
Me Me Me Me
HN +H+
MeO OMe Me MeO OMe MeO OMe
 Me Me Me Me Me Me
N N N
-MeO - -H +
Me Me Me
A B
MeO OMe MeO Me MeO NMe2
HN
Me

Me Me HO NHMe2 O
N
-MeO - OH2 - + -MeO -
H Me Me
Me
+H + -H +
Me2N Me2N
Me2N

Kozmin, S. A.' He, S.; Rawal, V. H. Org. Synth., Coll. Vol. Ⅹ 2004, 301.
A: Formation of an enamine to eliminate methoxide ion. B: Conjugate addition of dimethylamine to the
α,β-unsaturated iminium ion.

B047
H
Me Me Me Me
Me Me N N H
N -MeO- -H+
H OMe N OMe N OMe
A N +H+ B
MeO OMe

N
OBn H OBn OBn
H OMe
N -MeO-

O C O OMe
N N NO2
O O

MeO H
OBn H OBn Raney Ni OBn
N -H+ N NH2NH2 N
D E
NO2 NO2 NH2

OBn H OBn OBn

-MeO- N -H+
F +H+ H
NH2 N N N N
H H H
 OBn OBn
- N
H H -H+

G
N N
H H
Batcho, A. D.; Leimgruber, W. Org. Synth., Coll. Vol.Ⅶ 1990
Leimgruber-Batcho indole synthesis. A: Generation of an iminium ion under thermal conditions. B:
Replacement of dimethylamine with pyrrolidine. C: Generation of a benzylic carbanion stabilized by
o-nitro group. D: Formation of an enamine. E: Reduction of the nitro group. F: Protonation of the
enamine to form the reactive iminium ion. G: Elimination of pyrrolidine helped by the nitrogen lone
pair.

B048
ArO2S NC

ArO2S NC O C
O
N
H
A B
t-BuO K SO2Ar

H OEt
H
O N
O O
N N
H OEt SO2Ar
SO2Ar SO2Ar H OEt

H OEt

N OEt N
O O
Ar -ArSO2- CN
SO2Ar S
C O O

Oldenziel, O. H.; Wildeman, J; van Leusen, A. M. Org. Synth., Coll. Vol Ⅵ 1988, 41.
TosMIC (p-toluenesulfonylmethyl isocyanide). A: Deprotonation of an active methylene compound.
B: Intramolecular addition to the isocyanide to form an oxazoline anion. C: Loss of the activated formyl
group with a concomitant elimination of a toluenesulfinate ion ( pKa PhSO2H = 1.5).
B049
Ph3P Br
O
Br Br O
Ph3P Br C Br Br C H n-C7H15 Br
A Br n-C7H15
Br Br
Br

Li
PPh3
O n-Bu
Br Br BuLi Br
Br n-C7H15 n-C7H15 n-C7H15
B
Br Br Br
Ph3P

H Li
Li -LiBr
n-C7H15 n-C7H15 n-Bu H n-C7H15
C Br D

workup
Li n-C7H15 H n-C7H15
D +H+
Corey, E. J.; Fuchs, P. L. Tetrahedron Lett. 1972, 13, 3769
Corey-Fuchs reaction. A: Generation of a stable carbanion (cf. pKa CHCl3 = 13.6). B: E2 elimination
(triphenylphosphine oxide is an extremely good leaving group). C: Halogen-lithium exchange follow by
α-elimination to generate an alkylidene carbene. D: C-H insertion of the carbene. E: pKa n-Bu = 50,
-

RC≡CH = 25.

B050
Me ArSO2NHNH2 Me Me
O N SO2Ar BuLi N SO2Ar
Me Me N Me N
H
-H2O H
Me Me A Me Me Me Me
n-Bu Li
O O
Me Me -SO2Ar Me
N SO2Ar N S N
Me N Me N Ar Me N
B
H
Me Me n- u Me Me Me Me
B Li

O Ph Ph Ph Ph
-N2 Me Me workup Me
Me Ph Ph Me O Me OH
C +H+

Me Me Me Me Me Me
 Rupert, K. C.; Liu, C. C.; Nguyen, T. T.; Whitener, M. A.; Sowa, J. R.. J,
Organometallics 2002, 21,144
Shapiro reaction. A: Formation of a hydrazone. B: Deprotonation of the α-position of the hydrazone
anion. C: Elimination of a sulfinate ion ( pKa RSO2H = 1.5). D: Loss of N2 to form an alkenyl anion.

B051
H H H -CO2
O O O -H+ H
O O O
OH
Ar OH Ar OH A Ar OH B Ar

-H+ H HO CO2Me -H2O HO CO2Me

Ar +
+H+ NH2 +H+ N
O HO HO H

Ar

+H+ HO CO2Me -H+ HO CO2Me

C N NH
HO H HO
H
Ar Ar
Konda, M.; Shioiri, T.; Yamada, S. Chem. Pharm. Bull. 1975, 23, 1025
A: Generation of a stabilized benzyl cation. B: Decarboxylation to form an enol, an aldehyde
equivalent. C: Pictet-Spengler reaction ( ref A033).

B052
H
H O O
O H
O O OMe O O O O
H H
H H H
A B
O O O

O O O O -HCO2Me O O OH
O O
C +H+
OH
O H O HO H O
H
MeO H
MeO
Shimada, K.; Kaburagi, Y.; Fuku yama, T. J. Am. Chem. Soc. 2003, 125, 4048.
A: pKa MeOH = 15.5, CH 3CHO = 16.7. B: Aldol reaction. C: Intramolecular hydride transfer
(Cannizzaro-type reaction).
B053
O
O O O
OMe H
Me
OMe O OMe
N A Me B
N H N
N N
N

OH O OH O
-H+ Me Me
OMe OMe
+H+ C
N
N

Brown, J. M.; Evans, P. L.; James, A. P. Org. Synth., Coll. Vol. Ⅷ 1993, 420.
Morita-Baylis-Hillman reaction. A: Michael addition of DABCO. B: Aldol reaction. C: Elimination of
DABCO.

B054

N
O H N CO2Me N
O B
-H2O
A
OMe

N N
N OMe CO2Me
CO2Me
A O C

OH2
N N N
+
CO2Me aq HCl CO2Me CO2Me -H
H +H+

- H2
NH OH N O O
CO2Me H CO2Me Pd/Al2O3 CO2Me
-H+ MeOH
 Burpitt, R. D.; Thweatt, J. G. Org. Synth., Coll. Vol. Ⅴ 1973, 277.
A: Formation of an enamine. B: A stepwise formation of the four-membered ring by means of Michael
addition. C: Cleavage of the cyclobutene to release the ring strain.

B055
O O O O O O

Ph OEt Ph OEt Ph OEt

A B H
H N N N Ts N N
NEt3 N Ts

O O O O O O
-TsHN-
Ph OEt Ph OEt Ph OEt
N N C N N
N Ts
H N N
Lall, M. S.; Ramtohul, Y. K.; James, M. N. G.; Vederas, J. C. J. Org. Chem. 2002, 67, 1536.
+
Regiz Diazo transfer reaction. A: pKa RCOCH2CO2R = 11, HNEt3 = 10.7. B: Attack on the less
hindered, electrophilic nitrogen. C: pKa PhSO2NH2 = 8.5:

B056

Ts
N N
N OEt
t-BuO H
A
S S S

H OEt
Et H
OEt OEt O OEt OH2
N HN H2N
aq HCl H2N
+H+
S S B S S

H
EtO OH OH O
-H+ H3N H3N -H+ H3N
+H +
S S S

Dijkstra, D.; Rodenhuis, N.; Vermeulen, E. S.; Pugsley, T. A.; Wise, L. D.; Wikstrm, H. V.
J. Med. Chem. 2002, 45, 3022.
Neber rearrangement. A: Generation of a nitrene to form the azirine, which then undergoes addition of
ethanol. B: Acidic hydrolysis of the ethoxyaziridine.
B057
Me Me Me Me OEt
H
NaOEt
O O O O A
Br
Br Br Br Br
Br Br
Br

Me Me Me Me

OEt CO2Et
OEt
O O B
O
Br Br
Br Br

Marx, J. N.; Norman, L. R. J. Org. Chem. 1975, 40, 1602.

A: Favorskii rearrangement ( ref A069). B: Cleavage of the strained cyclopropanone with a
concurrent elimination of the bromide (formation of the thermodynamically more stable trans-ester).

B058
O O O O
I
I I I I
CO2Me A Me
O OMe O O O
H2O OMe OH H

O O O
HCl
I I I
O O B O
OH OH
O O O

O O O
OH H3C I

O O H O O O O
O O OMe

Shoji, M.; Yamaguchi, J.; Kakeya, H.; Osada, H.; Hayashi, Y. Angew. Chem. Int. Ed. 2002, 41,319;
A: Iodolactonization. B: Hydrolysis of the lactone followed by formation of the epoxide.
B059
O O
N
MeO2C MeO2C N
Cl
H

H2C N N H2C N N

Cl H3C N N ClCH3 + N2

O HBr O
N N
MeO2C N MeO2C N

O -N2 O
N
MeO2C N MeO2C Br

Br

Nair, V.; Jahnke, T. S. Tetrahedron 1987, 43 4257.

Excess diazomethane is needed to scavenge HCI.

B060
O O O O
O O
OH O O Me
Me O Me A
H
B
N N N O Me
Me Me H Me H
O

O O O O
-AcOH
O Me O Me
C OAc D
N O
N N N O
Me Me H
Me H H Me
Rueppel, M. L.; Rapoport, H. J. Am. Chem. Soc. 1978, 92, 5781.
A: Formation of a mixed anhydride. B: pKa (CH3CO)2O = 13.5. C: β-Elimination. D: Intramolecular
acylation is faster than intermolecular one.
B061
O
EtO P
CN
Me
NEt3 EtO CN R
O O
11
H R O P(OEt)2
A
Me OH O OH O O
OH O

-HCN H
R CN H2N CO2t-Bu Me N CO2t-Bu
B 11
OH O Me OH O
Shioiri, T.; Terao, Y.; Irako, N.; Aoyama, T. Tetrahedron 1998, 54, 15701.
A: Formation of a mixed anhydride. B: Formation of the reactive acyl cyanide.

B062
O O O -HCl
-POCl3
NH2 NH2 NH2
A Cl
N N N
Cl H
O Cl4P Cl O O
PCl4 PCl3
Cl

Cl4P Cl Cl
PCl3
O O -HCl
-HCl -POCl3 CN
NH2 NH
B
N Cl N Cl N Cl
Taylor, E. C., Jr.; Crovetti, A. J. Org. Synth., Coll. Vol. Ⅳ 1963, 166.
A: Activation of the N-oxide with PCl5. B: Dehydration of the amide.

B063
Cl Cl

O O
H
NC CN
O O
Me Me
OH OMe A OH OMe
Cl Cl

O O

NC CN
 O O
-H+ Me -H+ Me
OH OMe O
B
OMe
Crimmins, M. T.; Siliphaivanh, P. Org. Lett. 2003, 5, 4641.
A: Transfer of two electrons from the starting material to DDQ by forming a charge-transfer complex.
B: Deprotonation to form a p-quinonemethide-type intermediate.

B064
O
Cl S N C O H
O N O O N O
O S S
Cl O H Cl O
OMe OMe DMF OMe
O
A Me B
N H
OMe OMe Me OMe

Me Me Me
O N O N O N
O O O
O S Me O S Me O S Me
HN O N O N O CN
-SO3
OMe
OMe -H+ OMe OMe -DMF
C
OMe
OMe OMe OMe
Lohaus, G. Chem. Ber. 1967, 100, 2719.
A: Electrophilic substitution of an electron-rich aromatic compound. B: Attack on the oxygen of DMF.
C: Cyclization followed by fragmentation to form the nitrile.

B065
O O
CO2H CO2H -H+ H
O O
A +H+
NH2 N N O N N OH N N OH2
H
t-BuO N O
 O
C N C N
O
B C
N N Br Br
H OH

OH
HO O
N N -H+
N
D +H+ H
Br
Br Br
Rigby, J. H.; Laurent, S. J. Org. Chem. 1998, 63, 6742.
A: Formation of a diazonium salt ( ref A037). B: Formation of a benzvne with a loss of CO2 and N2.
C: Nucleophilic addition of the isocyanide. D: Addition of water to the nitrilium ion.

B066
AcO OAc
I
OAc
Ph
I
OH O Ph O
-AcOH -AcOH NaHCO3
-PhI MeOH
O O
A O
OH OH CbzHN
NHCbz NHCbz H O

O O
H
-H+ +H+
CO2Me
O +H+ OH B N
O
H Cbz
CbzHN OMe
O CbzN
H
O
MeO

Wipf, P.; Li, W. J. Org. Chem. 1999, 64, 4576.

A: Oxidative lactonization of N-Cbz tyrosine. B: Intramolecular Michael addition to the cross-
conjugated dienone.
B067
H
O
N C CCl3 N
H
O B O O CCl3
A

CO2Me
HO CO2Me
Me O
H H Me
NH N
TfOH -H + +
O CCl3 O CCl3 NH2
+H+ B
O CCl3

White, J. D.; Reddy, G. N.; Spessard, G. O. J. Am. Chem. Soc. 1988, 110, 1624.
A: Addition of benzyl alcohol to electron-deficient Cl3CCN with a help of catalytic amount of base. B:
Ftherification of alcohols under acidic conditions.

B068

H
+H+ -H2O
Me OH Me OH2 Me Me
Me Me A
Me Me Me

O H O O O
-H2O -H+
H C
H OH H O
H B
H

Me Me O
Me Me
- H C
Me
Me
H
C

OH2
-H+
C O OH
D
O

Koch, H.; Haaf, W. Org. Synth., Coll. Vol. Ⅴ 1973, 20.

A: Formation of a stable t-butyl cation. B: Generation of CO by dehydration of formic acid. C:
Hydride abstraction from the bridgehead of adamantane. D: Addition of CO to form an acylium ion.
B069
t-BuO
H

Ph O Ph Ph O Ph Ph O Ph
A B

Ph Ph -H+ Ph
Ph Ph
O Ph +H +
C
OH OH
Hauser, C. R.; Kantor, S. W. J. Am. Chem. Soc. 1951, 73, 1437.
[1,2] Wittig rearrangement. A: pKa PhCH3 = 41, n-BuH = 50. B: Homolytic cleavage to form a radical
anion. C: A facile radical recombination in a solvent cage.

B070
OMe
O Ph
Ph N H
H O
O A
Ph N

Ph O
C - workup
H OMe PhCN Ph Ph
O CO2Me CO2Me
+H +
N B
O O
Ph
Gómez, V.; Perez-Medrano, A.; Muchowski, J. M. J. Org. Chem. 1994, 59, 1219
A: Michael addition of an oxime anion. B: Intramolecular deprotonation to cause fragmentation.

B071
n-Bu3Sn
S n-Bu3SnS
N N
N N
O O
AIBN
n-Bu3SnH
O O
n-Bu n-Bu

Me

O O
A B H C
n-Bu OH
Me
 H Me H Me
n-Bu3Sn H - n-Bu3Sn

D
OH OH
Rawal, V. H.; Newton, R. C.; Krishnamurthy, V. J. Org. Chem. 1990, 55, 5181.
A: Barton-McCombie deoxygenation ( ref A051). B: Cleavage of the strained epoxide ring. C:
Intramolecular abstraction of a hydrogen via a six-membered transition state. D: 5-exo-trig Radical
cyclization.

B072
Br SO2CH2Br
O Br hv Me Me
Br S
A B
O SO2CH2Br
SO2CH2Br H

Br Br
-SO2CH2Br Me t-BuOK Me

C D
SO2CH2Br SO2CH2Br
H H
Ot-Bu

H Ot-Bu
CH2 -SO2

S Br
S
O O
O O
Block, E.; Aslam, M. Org. Synth., Coll. Vol. Ⅷ 1993, 212.
A: Photo-induced homolytic cleavage to form a sulfinyl radical. B: Addition to the olefin to form a
stable tertiary radical. C: Attack on the bromide of the reagent (radical chain reaction). D: Elimination
of HBr followed by vinylogous Ramberg-Bäcklund reaction.

B073
Me Me KNH2 Me Br hv Me Br
+ +
O O A O
 Br

Br Me

Me

O D C

Me

Br

Rossi, R. A.; Bunnett, J. F. J. Org. Chem. 1973, 38, 3020.

SRN1 reaction. A: SET to bromobenzene to form a radical anion. B: Fragmentation of the radical
anion to form a phenyl radical. C: Addition to enolate to form a radical anion. D: SET to continue the
radical chain reaction.

B074
S
O O
N Bu hv Bu -CO2 Bu
O N O N N
A B F3B C

O
F3B Bu N Bu
Bu O N
N N CH2
F3B S
D E

N CH2
F3B Bu

O
N Bu Bu
O N F3B Bu N N
workup
S N N
N S S
F
F3B Bu
 Newcomb, M. Ha, C. Tetrahedron Lett. 1991, 32, 6493.
A: Photo-induced homolytic cleavage. B: Decarboxylation to form an aminyl radical. C: Acti vation of
the aminyl radical by Lewis acid. D: Kinetically fa vored 5-exo-trig radical cyclization. E: Group
transfer reaction.

B075
-Br-
t-BuO H CBr3 CBr2 CBr2
A Br B

Me Me
Me
Br MeLi Br
CBr2
Br Br
Me C D
Me Me
Me

Me Me Me
Br -Br- H Me
Me
E Me
Me Me
Taylor, R. T.; Paquette, L. A. Org. Synth., Coll. Vol.Ⅷ 1990, 200.
A: pKa CHCl3 = 13.6. B: α-Elimination to form dibromocarbene. C: Cyclopropanation of the more
electron-rich, tetrasubstituted olefin. D: Halogen-lithium exchange and subsequent α-elimination to
form a carbene. E: C-H insertion of the carbene (the corresponding allene cannot be formed due to
the excessive ring strain. ref A061).

B076
Cl
O O OEt
-Cl- Cl
Cl Cl Cl
OEt OMe
Cl Cl A Cl B
Cl Cl Cl
OMe

Cl
Cl
Cl
Cl
C D
Cl Cl

Jefford, C. W.; Gunsher, J.; Hill, D. T.; Brun, P.; Gras, J. L.; Waegelt, B.
Org. Synth., Coll Vol. Ⅵ 1988, 142.
A: pKa CHCl3 = 13.6. B: Generation of dichlorocarbene. C: Cyclopropanation from the sterically less
hindered exo-side. D: 2e Disrotatory electrocyclic reaction to form an allyl cation.
B077
O
H
O O O CCl3 OH
Cl -CO2 O Cl
O H
Cl A Cl Cl Cl
Cl Cl Cl
Cl Cl
Cl

OAc OAc
Ac2O Cl Zn Cl Cl MeLi
Cl B Cl C
Cl Cl Cl
Zn

H
OMe
Cl

Cl Cl

OMe workup
H H
+H+
Wang, Z.; Campagna, S.; Xu, G.; Pierce, M. E.; Fortunak, J. M.; Confalone, P. N.
Tetrahedron Lett. 2000, 41, 4007.
A: pKa CHCI3 = 13.6. B: Reduction with Zn to form a gem-dichloroolefin. C: Corey-Fuchs-type
alkynylation ( ref B049).

B078
H SiMe3 SiMe3
O +
-H H H
H H H2O N
+H + Bn N A NHBn
Bn
H2N Bn

H
OH2 O
Me3Si
H H -H+ OH2

NHBn B NHBn +H+ NBn

OH2 OH
-H2O -H+
NBn C NBn NBn
H H
 Larsen, S. D.; Grieco, P. A.; Fobare, W. E J. Am. Chem. Soc. 1986, 108, 3512.
A: Addition of an allylsilane to the iminium ion (a silyl group can stabilize the β-carbocation). B:
Desilylation to form an olefin. C: Olefin-iminium ion cyclization to form a stable tertiary carbocation.

B079
O
O CO2Et
S
CO2Et HN N
N NH2
N N EtO2C PPh3
NO2 H
EtO2C A CO2Et B
Ph3P N N HO
EtO2C PPh3

CO2Et O
O
HN N S
EtO2C N NH2 - Ph3P O
NO2
H
O O
PPh3 PPh3

O2N -ArSO2H -N2

O S C D
N N
O H
NH2 N
H

Myers, A. G.; Zheng, B. Tetrahedron Lett. 1996, 37, 4841.

A: Mitsunobu reaction ( ref A045). B: Deprotonation of the more acidic proton. C: Elimination of a
sutfinate ion. D: Elimination of N2 via a concerted mechanism.

B080
PPh3
O O PPh3 O
PPh3
CO2Et
H CO2Et CO2Et
A
NO2 NO2 NO2

CO2Et CO2Et
P(OEt)3
O B
NO2 N
P(OEt)3
O
 CO2Et CO2Et CO2Et

O C O
N O N P(OEt)3 N P(OEt)3
O P(OEt)3

CO2Et

H D
N N CO2Et
H

CO2Et CO2Et CO2Et

A N
N N

H
N CO2Et N CO2Et
H
Mali, R. S.; Yadav, V. J. Synthesis 1984, 862.
A: Wittig reaction. B: [4+2] Cheletropic reaction and elimination of a phosphate to form a nitroso
intermediate. C: Deoxygenation of the nitroso compound to form a nitrene. D: Formation of the
indole could be interpreted as a result of either 1) a direct C-H insertion or 2) formation of the azirine
followed by homolytic cleavage and recombination of the resulting diradical.

B081
H
O O
O H
+
N N +
O N -H O -H O -H+ OH2
OH2 N N
N
OH +H+ H2N CO2H +H+ HN CO2H +H+ N CO2H
H H H
Me Me Me

H
N OH O
-H2O N -N2
H Cl CO2H
O O
H A B H
Me Me Me
Cl
Koppenhoefer, B.; Schurig, V. Org. Synth., Coll. Vol.Ⅷ 1993. 119
A: Formation of a very reacti ve α-lactone via a diazonium salt. B: Cleavage of the α-lactone with
chloride ion. The stereochemistry of the α-position is retained as a result of the double inversion.
B082
O
CO2Et
Me
MeO NaNO2 MeO Et
HCl KOH
NH2 N N
A

O
CO2Et OH
MeO Me MeO O Me
O
Et
N N B N N
Et OEt C
HO H

MeO MeO H Me
Et aq HCl -H+
N N CO2Et EtOH N N CO2Et D
H H H
65oC
Me
H
MeO Me MeO CO2Et
-H+
NH
N N CO2Et NH +2H+
H H
H
Me
MeO CO2Et MeO Me
-H+ -NH3
NH CO2Et
NH2 2 +2H+ N
H NH3

MeO Me MeO Me
H -H+

N CO2Et N CO2Et
H H
Zhao, S.; Liao, X.; Wang, T.; Flippen-Anderson, J.; Cook, J. M.
J. Org. Chem. 2003, 68, 6279.
Japp-Klingemann reaction and Fischer indole synthesis. A: Formation of a diazonium salt. B:
Addition of the enolate to the diazonium salt. C: Ketone cleavage of β-ketoester to form a hydrazone.
D: Fischer indole synthesis ( ref B031).
B083
O O Ph
N N -N2
N N C6H13
Ph Ph O
A B
B(C6H13)2 (C6H13)2B
B(C6H13)2 C6H13
C6H13

Ph workup O
C6H13 B(C6H13)2 C6H13
C O +H+ Ph

Kono, H.; Hooz, J. Org. Synth., Coll. Vol. Ⅵ 1988, 919.

A: Attack of a diazoketone to B(n-hexyl)3 to form an ate complex. B: Elimination of N2 with a
simultaneous migration of n-hexyl group. C: Formation of a boron enolate.

B084
H
O H2O OMe OMe
-H + -H+
Me Me
+H+ H
i-Bu HOMe i-Bu i-Bu

MeOH -MeOH

MeO OMe
Me

i-Bu

OMe OMe MeO OMe

I I I -H+ I AgNO3
A
i-Bu i-Bu HOMe i-Bu

HOMe
MeO OMe
OMe -H+ OMe
B C OMe MeO OMe
i-Bu i-Bu i-Bu

OH2
H2O OMe -H+
OMe
+H+ MeO OMe +H+
i-Bu OMe
D H i-Bu
 OMe OMe
HO OMe O
i-Bu i-Bu
H
Oppolzer, W.; Rosset, S.; Brabander, J. D. Tetrahedron Lett. 1997, 38, 1539.
A: Iodination of the enol ether with concomitant formation of a dimethyl acetal. B: Activation of the
iodide with a silver ion to form a phenonium ion. C: Restoration of the aromaticity causes a cleavage
of the electron-rich cyclopropane ring. D: The orthoester thus formed undergoes a facile hydrolysis to
give the ester.

B085
O O O -AcOH O
HO S OH AcO S OH S O
AcO Me A O
O O

Me Me Me Me Me Me

B
Me Me
O O OH
H H

Me Me Me Me Me Me
-H+

C
OH OH O
O SO3H SO3H
S OH
O
Bartlett, P. D.; Knox, L. H. Org. Synth., Coll Vol Ⅴ 1973, 194.
A: Generation of SO3. B: Wagner-Meerwein-type rearrangement. C: Sulfonation of the olefin to form
a stable tertiary carbocation.

B086
OMs OMs OMs
Me Me Me
NaOH
A H2O
H H H
H2B H2B (HO)3B
 H
Me
H OMs
H
Me
B
H
(HO)3B H H

Marshall, J. A.; Bundy, G. L. J. Am. Chem. Soc. 1966, 88, 4291.

A: Hydroboration from the less hindered side. B: Grob fragmentation ( ref B016).

B087
Me Me Me
Br
Br
O Br O O
Br A Br
Me Me Me
Br

t-BuO H
Me Me Me
Br
t-BuOK
O O O
Br B C
Me Me Me
H
t-BuO

Paquette, L. A.; Barrett, J. H. Org. Synth., Coll. Vol.Ⅴ 1973, 467.

A: Bromination of the olefin. B: Dehydrobromination to form a diene. C: 6e Disrotatory electrocyclic
reaction (valence isomerism).

B088

-H+ H -H+
N N
H +H+
O OH N

N
N -N2
N
N N A N B N C
H
N N N N

Golka, A.; Keyte, P. J.; Paddon-Row, M. N. Tetrahedron 1992, 48, 7663.

A: Inverse electron demand Diels-Alder reaction. B: Retro Diels-Alder reaction. C: Aromatization.
B089
O H NEt3 O O H NEt3
N N N

H Cl Cl
H
A

Cl O H OH Cl OH

O
N O N O
N
Cl
B C D

Lee, G. A. Synthesis 1982, 508.

A: Chlorination of an oxime. B: Elimination of chloride ion is facilitated by the formation of an oxime
anion. C: Generation of a nitrile oxide. D: 1,3-Dipolar cycloaddition.

B090
O O O
N Me N Me N Me
O O O
H A B H
O C NPh O N
Et3N
Ph

N Me
O O
N
C Me D
AcO AcO

or

O
O
N Me O N
O N Me
C Me
H
O N H
Ph

O +H+ -H+ O
Ph Ph N C O Ph Ph
N O -CO2 +H+ N N
H Ph NH2 H H

Mukaiyama, T.; Hoshino, T. J. Am. Chem. Soc. 1960, 82, 5339.

A: pKa CH3NO2 = 10.2, HNEt3+ = 10.7. B: Addition of the nitronate to PhNCO. C: Formation of the
nitrile oxide might proceed either by 1) syn-elimination of the carbamate ion or 2) elimination of the
carbamate ion followed by deprotonation. D: 1,3-Dipolar cycloaddition.
B091
Me
OEt +H + OEt -EtOH OEt
H3C OEt H3C OEt H3C O
A OEt
OEt OEt H Me
H

Me H Me
CH3
-H+ EtO -EtOH -H+
+H+ EtO O EtO O B
H Me Me

Me EtO EtO Me
O R O R
EtO O C EtO O
Me Me
Me Me
Johnson, W. S.; Werthemann, L.; Bartlett, W. R.; Brocksom, T. J,; Li, T.-t.
J. Am. Chem. Soc. 1970, 92, 741.
Claisen-Johnson rearrangement. A: Acid-catalyzed ether exchange of the orthoester. B: Formation
of the mixed ketene acetal is effected by removal of ethanol from the reaction system by distillation. C:
[3,3] Sigmatropic rearrangement via a chair-like transition state to form an (E)-olefin.

B092
O OMe OMe
OH2 Me Me
Ph H -H+
Ph N
+H+ Ph N A Ph N
HN n-Pr Me OMe
n-Pr n-Pr
n-Pr Me OMe

H
MeO O H O
MeO
Me Me -H+ Me
-H+ -MeOH
Ph OH2 Ph Ph
B N +H+ N N
n-Pr n-Pr n-Pr

Overman, L. E.; Kakimoto, M.; Okazaki, M. E.; Meier, G. P.

J. Am. Chem. Soc. 1983, 105, 6622.
A: Aza-Cope rearrangement. B: Intramolecular Mannich reaction.
B093
t-Bu OTf
Si Me Me
Me Me Si
O Et3N O t-Bu OTBS
H
O O O
A

OMe OMe OMe

OMe OMe O
H H OMe
O H TBSO
O
B
TBSO OSBT

Me HO
t-Bu
H3O+ Si OMe HO2C OMe
Me O
H2O

Nakatsuka, M.; Ragan, J. A.; Sammakia, T.; Smith, D. B.; Uehling, D. E.; Schreiber, S. L.
J. Am. Chem. Soc. 1990, 112, 5583.
Claisen-lreland rearrangement. A: Formation of a ketene silyl acetal. B: [3,3] Sigmatropic
rearrangement via a boat-like transition state.

B094

Me Me O Me O
S
H Ph A S
Ph
O H O O

workup Me O 150oC Me O
H
+H + S S
Ph Ph
O O

Me
CHO
B C Me
O
Saito, M.; Kawamura, M.; Ogasawara, K. Tetrahedron Lett. 1995, 36, 9003.
A: Conjugate addition to the vinyl sulfoxide. B: syn-Elimination. C: Claisen rearrangement.
B095

Br
n-BuLi
Br S S S
A A
S S H S
n-Bu

HgCl2
S S S
H2O
S S C S
Cl Hg Cl

HgCl
-H+ S
S S
H2O S
S S CHO
Hg Hg
OH
Cl Cl
Hunt, E.; Lythgoe, B. J. Chem. Soc., Chem. Commun. 1972, 13, 757.
A: Formation of a sulfonium ion. B: Deprotonation to form a sulfur ylide, which undergoes [2,3]
sigmatropic rearrangement. C: Hydrolysis of the thioacetal.

B096
CHO CHO CHO

H B
O O Br O

H
N CO2Et CO2Et
Me
H Me
N CO2Et O N
Me -H +
H OH
+H+
O O
CO2Et CO2Et
Me CO2Et
Me Me
N H OH N N
H

A B H
O O O
Bashiardes, G.; Safir, I.; Mohamed, A. S.; Barbot, E; Laduranty, J. Org. Lett. 2003, 5, 4915.
A: Formation of an azomethine ylide. B: Intramolecular 1,3-dipolar cycloaddition.
B097
Me Me Me
AcO AcO AcO
hv
Me Me Me
AcO A AcO AcO
H H H
Me O Me O Me O
H OAc N OAc N OAc
N O O O
Cl
O N
H
O OH
AcO AcO
AcO AcO
B C
Me Me
H H
O
H N NOH
AcO -H+ AcO
D Me +H+ Me
AcO E AcO
H H
Me OH Me OH
OAc OAc
Murai, A.; Nishizakura, K.; Katsui, N.; Masamune, T. Tetrahedron Lett. 1975, 16, 4399.
Barton reaction. A: Formation of a nitrite. B: Homolytic cleavage. C: Abstraction of a hydrogen
atom via a six-membered transition state. D: Recombination of ,NO with the resulting radical. E:
Tautomerization.

B098

O O O O HO O
O N O H N O N
hv
Ph O Ph O Ph O
A B

O OH OH
O N O O N -H+
Ph O C Ph O +H+
D

O
O O N

Ph + H
O

Barltrop, J. A.; Plant, P. J.; Schofield, P. Chem. Commun. 1996, 822.

Photo-cleavable protecting group for acids. A: Photo-activated formation of a diradical. B:
Intramolecular abstraction of a hydrogen atom. C: Recombination of the diradical. D: Elimination of
benzoic acid.

B099
O
P OEt)2 O O H
O H2C ( O O O
O
A P(OEt)2 P(OEt)2
O
O O
P(OEt)2 P(OEt)2
O O
Me O Me O Me O
B

Altenbach, H.-J.; Holzapfel, W.; Smerat, G.; Finkler, S. H. Tetrahedron Lett. 1985, 26, 6329.
A: Addition to the reactive enol lactone. B: Intramolecular Horner-Wadsworth-Emmons reaction ( ref
A071 ).

B100
CHO CHO PPh3 Br
N A N B
H
H
O
O
N C N N
PPh3 PPh3

Schweizer, E. E.; Light, K. K. J. Org. Chem. 1966, 31, 870.

A: pKa of the parent indole NH = 17, H 2 = 35. B: Addition to the vinylphosphonium salt to form an ylide.
C: Intramolecular Wittig reaction.

B101
N
N PPh3 N N PPh3
PPh3
N N PPh3 N HO N
-N2
Ph Ph Ph Ph H
Ph Ph Ph
A B H Ph
OH OH OH
Ph3
P H OR H
-H+ O NH H NH2 -Ph3P=O N
Ph H H
+H+ Ph H H D
H Ph Ph3P O Ph Ph Ph
C
 Pöchlauer, P.; MüIler, E. P.; Peringer, P. Helv. Chim. Acta 1984, 67, 1238.
Staudinger reaction (A-B). A: Cheletropic reaction. B: Formation of an iminophosphorane. C:
Migration of the phosphorus group. D: Intramolecular SN2 reaction.

B102
Ph3P
H
O + O HO H HO Se
H H +H H H Ph -H+
H H Ph
Ph Ph Ph Ph A Ph Se PPh3 Ph H +H+
Ph3P Se B

PPh3 -H+
O SeH H SeH -Ph3P=O Se H -Se
Ph H
H Ph H Ph Ph D Ph Ph
Ph H Ph3P O Ph C

Clive, D. L. J.; Denyer, C. V. J. Chem. Soc., Chem. Commun. 1973, 253.

A: Acid-catalyzed cleavage of the epoxide with inversion of configuration. B: Migration of the
phosphorus group. C: Intramotecular SN2 reaction with inversion of configuration to form a cis-
episelenide. D: Spontaneous extrusion of selenium.

B103
N S N
NH S
S N N N
HO OH -H+ HO O HO O
N N N N
+H+
Ph Ph
Ph Ph Ph Ph

HN P(OMe)3
S S
N S
-H+ P(OMe)3
O O O O O O
+H+ A
Ph Ph Ph Ph Ph Ph

S P(OMe)3

O O O O -CO2

B C Ph Ph
Ph Ph Ph Ph

or
 P(OMe)3 P(OMe)3
-CO2
O O O O -P(OMe)3

C Ph Ph
Ph Ph Ph Ph
Corey, E. J.; Winter, R. A. E. J. Am. Chem. Soc. 1963, 85, 2677.
Corey-Winter olefination. A: Formation of a thionocarbonate. B: Reductive desulfurization of the
thionocarbonate to generate a carbene. C: The resulting carbene might undergo a direct
fragmentation to form the cis-olefin. Alternatively, it would react with a phosphite to form an ylide,
which then collapses to give the product.

B104
I SiMe3 Me3Si I
SiMe3
O O Me3Si O H
C8H17
H
C8H17 C8H17 A C8H17 C8H17 B C8H17 I

SiMe3
Me3Si O H
C8H17
C H D C8H17 C8H17
C8H17 I
I
Denis, J. N.; Magnane, R.; Eenoo, M. V.; Krief, A. Nouv. J. Chim. 1979, 3, 705.
A: Silylation of the epoxide. B: SN2 reaction with inversion of configuration. C: Silylation of the silyl
ether. D: E2 elimination.

B105
OMOM OMOM Me Me
C6H13 PdLn C6H13 Si Ln
O Pd H
H
O H A O Pd B
Si Si Ln C6H13 H
Me Me Me Me OMOM
Ln
MOMO Pd H MOMO H H2O2 OMOM
C6H13 -PdLn C6H13 KOH C6H13
O Si Me C O Si Me O Si OOH D
Me Me Me Me
 OMOM OMOM OMOM
C6H13 C6H13 C6H13
workup
O Si O OH E O O +H+ OH OH
Me Me Si
Me Me

Tamao, K.; Nakagawa, Y.; Arai, H.; Higuchi, N.; Ito, Y. J. Am. Chem. Soc. 1988, 110, 3712.
Tamao oxidation (D-E). A: Oxidative addition to the Si-H bond. B: Intramolecular diastereoselective
silametallation to the olefin. C: Reductive elimination. D: Formation of a silicate ion. E: Migration of
the Si-C bond.

B106
PhS Cl
Me Me Me Me
Me Me
O H O

NEt3
Me Me

Me Me Me Me Me Me
Me
O Me
SPh
A A B
Me Me Me
Me
SPh
SPh
O
O
Okamura, W. H.; Peter, R.; Reischl, W. J. Am. Chem. Soc. 1985, 107, 1034.
A: [2,3] Sigmatropic rearrangement of the propargyl sulfenate. B: 6e Disrotatory electrocyclic reaction.

B107
O O O SmI2
SmI2
MeO I SmI2 MeO I MeO
Me Me Me
O O A O

I2Sm I2Sm
O SmI2 O
OMe O

O O O
B
Me Me Me
 SmI2 SmI2
I2Sm I2Sm Me
O O HO
workup
O O O
Me Me +H+ Me
Molander, G. A.; Harris, C. R. J. Org. Chem. 1997, 62, 2944
A: Since Sml2 is a single electron reductant, two molecules of Sml 2 are needed to convert an alkyl
iodide to the corresponding organosamarium species. B: SET to the ketone followed by radical
cyclization.

B108
MeO OMe MeO OMe
Me Me

TfO
A
Hg TfOHg
TfO
Me Me

MeO OMe MeO OMe

Me Me

B C H
TfO Hg TfO Hg
H
Me Me
MeO OMe MeO OMe
Me Me

TfO D
TfO Hg
H H
Me Me
H
Imagawa, H.; lyenaga, T.; Nishizawa, M. Org. Lett. 2005, 7, 451.
A: Coordination of Hg(OTf)2 to the alkyne. B: 6-endo-dig cation cyclization to form a stable
tertiarycarbocation. C: Attack of the electron-rich aromatic ring to the carbocation. D: Protonolysis
of the C-Hg bond to regenerate the catalyst.
B109
- Ph
O O
MeO2C H MeO2C H
A

RuLn RuLn
Ph
Ph
MeO2C
MeO2C
O LnRu O
MeO2C O N N
LnRu H LnRu H H
B
R

MeO2C MeO2C
O O
LnRu N N + RuLn
H H R
R
Kinoshita, A.; Mori, M. J. Org. Chem. 1996, 61, 8356.
Intramolecular enyne metathesis ( ref A078). A: Intermolecular alkene metathesis. B: Intra-
molecular alkyne metathesis.

B110
O
CHO CHO
N A N B N C
H
SMe2
SMe2
H

O Na3N
N D N O N O E
SMe2

N3 +H+
N3 N3
N N N
O O OH

Wang, Y.; Zhang, W.; Colandrea, V. J.; Jimenez, L. S. Tetrahedron 1999, 55, 10659.
A: pKa indole NH = 17, H 2 = 35. B: Addition of the vin ylsulfonium salt to form an ylide. C:
Intramolecular addition to the aldehyde (reversible). D: Intramolecular SN2 reaction to form an epoxide.
E: Cleavage of the epoxide helped by the indole nitrogen lone pair.
B111
n=1
Ph Ph
N N N O
H N N N
O N OH N N -N2
N
O Me
Me Ph A Me Ph B
Me

n=3

N N
N N
O H N O HN
-N2
Me Ph Me
+H+
C

O
H H
O OH N
NH Me
Me Me
D NHPh
H

Wrobleski, A.; Aube, J. J. Org. Chem. 2001, 66, 886.

Intramolecular Schmidt reaction. A: Acti vation of the carbonyt group by protonation followed by
intramolecular addition of the azide (six-membered ring is easy to form). B: Ring contraction. C: The
formation of a phenonium ion is preferred over the formation of the eight-membered ring. D:
Intramolecular Mannich reaction.

B112

N O N N
Tol S S STs S S
O A H STs S B
NEt3 O S O
Tol

Et3N N N N N
S S aq HCl H S H2O S
H
S S C S S
 N N H - N O
H2O S -H+ O S H S

S +H+ S -H+ S

Woodward, R. B.; Pachter, I. J.; Scheinbaum, M. L. Org. Synth., Coll. Vol. Ⅵ 1988, 1014.
A: pKa PhSO2H = 1.5. B: Formation of an easy to form six-membered ring. C: Hydrolysis of the
enamine.

B113
Ph O Ph
Ot-Bu
H Me
O O H O O
AcN AcN O N
NAc A NAc NAc B
O O O
Ph O O Ph AcO Ph
O
Me H Ot-Bu
O Me O O
O N N HN
t-BuO H
NAc NAc NAc
O O O

AcO Ph Ph
Ph H
O H N O O
HN HN
C
NAc OAc NAc
O O

Gallina, C.; Liberatori, A. Tetrahedron Lett. 1973, 1135.

A: Deprotonation of the α-position of an imide (more acidic than amides). B: Aldol reaction followed by
an intramolecular acyl transfer via a five-membered ring transition state. C: Elimination of the acetoxy
group.

B114
O R O
H H
O OH O R O
O
-H+
Me Me C Me C O O
Me A C Me +H+
N N
Me2N R
Me Me
 Me Me Me
Me N Me N Me N
Me Me Me CSA
O O O O O B O O O toluene
R R O R

Me Me
OH Me N OH Me N
Me Me
O O C O O
H
O H O
Me Me
Me N Me N
O + Me Me
O OH O O
O
Gais, H. J. Tetrahedron Lett. 1984, 25, 273.
A: Protonation of the carbonyl group followed by addition of the carboxylate to the iminium ion. B:
Intramolecular acyl transfer to form a vinylogous anhydride. C: Acti vation of the vin ylogous anhydride
by protonation resulted in the formation of the macrocyclic lactone.

B115
OEt OEt OEt OEt
O O e
e O O
O A O B
O
OEt OEt EtO O

OEt OEt e
O O
Me3Si Cl
O O C
O O
O O

O SiMe3 O SiMe3 O SiMe3 OSiMe3

e
D
O O O Me3Si Cl OSiMe3

Bloomfield, J. J.; Nelke, J. M. Org. Synth., CoIl Vol. Ⅵ 1988, 167.

Acyloin condensation. A: Single electron transfer (SET) to the carbonyl group followed by
lactonization. B: SET followed by a ring contraction. C: SET followed by silylation. D: SET to form
an enolate followed by silylation.
B116
O O O -H+
O O +H+
A B
O O O C
O
MeOH
H H H
O O O
TsOH -H+
O O
HO H HO H +H+ R OMe
D
OMe OMe MeOH

MeOH
OMe
-H+ NaHCO3
O
R OMe HO OMe
Me2S
OMe E

Me2S -H+ OMe

O R HO R -MeOH
HO O
+H+ OMe
OMe OMe
F H
Claus, R. E.; Schreiber, S. L. Org. Synth., CoIl Vol. Ⅶ 1990, 168.
A: 1,3-Dipolar cycloaddition of ozone to the olefin. B: Heterolytic cleavage of the initial ozonide. C:
Trapping the dipole with methanol. D: Formation of a dimethyl acetal from the aldehyde (protonation
of the less electron-dense hydroperoxy group is more difficult). E: Neutralization to kill TsOH. F:
Reduction of the hydroperoxide with dimethyt sulfide.

B117
O O O -H+
O O +H+
A B
O O O C
O
MeOH
NEt3
O O
O Ac2O O H
H OH H O
Et3N
OMe OMe

O O
NEt3
Me O Me O O
H
R O R O O
O O Me H
D E
OMe OMe OMe

or
 NEt3
O H O
H
R O R O O
O Me H
E
OMe OMe OMe

or
O Me O
H
O
R O E H
MeO O
OMe

Claus, R. E.; Schreiber, S. L. Org. Synth., CoIl VoL Ⅶ 1990, 168

A: 1,3-Dipolar cycloaddition of ozone to the olefin. B: Heterolytic cleavage of the initial ozonide. C:
Trapping the dipole with methanol. D: Acetylation. E: Elimination of acetic acid might proceed either
by 1) deprotonation with triethylamine, 2) Baeyer-Villiger-type 1,2-hydride shift, or 3) thermal eliminatior
via a six-membered transition state.

B118
AIBN
n-Bu3Sn X n-Bu3SnH n-Bu3Sn
A
H
X=Cl or I

OEt OEt
I Snn-Bu3
O O
-n-Bu3SnI

OEt OEt OEt

O O O
-t-Bu

C H
C N C N CN
Me
t-Bu
e
M Me

Stork, G.; Sher, P. M. J. Am. Chem. Soc. 1986, 108, 303.

A: Reduction of Bu3SnX with NaBH3CN to form a low concentration of Bu 3SnH to avoid the premature
reduction of the radical intermediates. B: 5-exo-trig Radical cyclization. C: Addition to the isocyanide
followed by elimination of a stable t-butyl radical.
B119

N N
N N
F3B N N N N
N
O

A OBF3 B OBF3

N N
-N2
N O
BF3 BF3
C O D O E

Lang, S.; Kennedy, A. R.; Murphy, J. A.; Payne, A. H. Org. Lett. 2003, 5, 3655.
A: Generation of a stable benzylic carbocation. B: Intramolecular attack of the azide. C: formation
ofan aziridine. D: Restoration of the aromaticity. E: 1,2-Alkyl shift.

B120
Ph N O

Ph Ph O Me
N N N
Cl O H Cl O A B
NEt3 O

Ph N
O O
O Me
N N Ph
C Ph N D O
O
O O

Quadrelli, P., Mella, M.; Invernizzi, A. G.; Caramella, P. Tetrahedron 1999, 55, 10497.
A: Elimination of chloride ion is facilitated by the formation of an oxime anion. B: Addition of NMO to
the nitrile oxide. C: Generation of an acylnitroso compound. D: Hetero-Diels-Alder reaction.

B121
H
O O O H
H -H+
+H+ B
A
 H
O O
-H+
+H+ B
A

Drouin, J.; Leyendecker, F.; Conia, J., M. Tetrahedron. 1980, 36, 1203.
A: Tautomerization. B: Oxy-ene reaction.

B122
Me Me Me Me Me Me

-N2

H A B C
OO N O N O
S N S O SO2
O N
Cl CH2 O
NEt3

Me Me Me Me Me Me Me Me

95oC -SO2

D
O O O O
SO2 SO2 SO2

Fischer, N.; Opitz, G. Org. Synth., Coll. Vol. Ⅴ 1973, 877.

A: Generation of a sulfene. B: 1,3-Dipolar cycloaddition of diazomethane to the sulfene. C:
Extrusion of N2 to form an episulfone. D: Ramberg-Bäcklund reaction.

B123
PPh3Br PPh3
A
H

t-BuO K

O O O
PPh3 PPh3
PPh3
B C D

H
 Ph

+ O Ph
E
O Ph
O
PPh3 Ph

Dauben, W. G.; Ipaktschi, J. J. Am. Chem. Soc. 1973, 95, 5088.

A: Generation of an ylide. B: Michael addition. C: Regeneration of a phosphorus ylide. D:
Intramolecular Wittig reaction (irreversible). E: The unstable diene was trapped as the Diels-Alder
product.

B124
OTBS
Cl SePh
O Me Me
O PhSeCl O
Me
A B
OTBS OTBS

HO OH
PhSe Me PhSe Me PhSe Me
aq H2O2
O O O
Sit-BuMe2
H H H
Cl

OH
H Ph Ph
O Se Me O Se Me Me
-PhSeOH
O H O O
H C
H H H
Curran, D. P.; Rakiewicz, D. M. Tetrahedron 1985, 41, 3943,
A: Claisen-lreland rearrangement. B: Selenolactonization. C: syn-Elimination of the selenoxide.

B125
O Ph O Ph
Ph S
hv
Ph S H Ph Ph S Ph S
Cl
O
B
 O Ph HO Ph Ph
H S
A Ph S B Ph S S C
Ph
Vedejs, E.; Eberlein, T. H.; Ma zur, D. J.; McClure, C. K.; Perry, D. A.; Ruggeri, R.; Schwartz, E.;
Stults, J. S.; Varie, D. L.; Wilde, R. G.; Wittenberger, S. J. Org. Chem. 1986, 51, 1556.
Norrish type II reaction. A: n-π* Transition. B: Intramolecular abstraction of a hydrogen atom
followed by fragmentation to form a highly reactive thioaldehyde. C: Hetero-Diels-Alder reaction.

B126
Me O Me O
Me -N2
Me
RuLn
N N A
AcO RuLn AcO
N N
Me Me Me
-RuLn
O AcO
O B C
AcO AcO Me
Ru Me O
Me
Ln
Kennedy, M.; McKerve y, M. A. J. Chem. Soc., Perkin Trans. Ⅰ1991, 2565.
A: Formation of a rhodium carbene complex. B: C yclopropanation of the aromatic ring. C: 6e
Disrotatory electrocyclic reaction.

B127
Ph
Ph
Cr(CO)5 (CO)4Cr (CO)4Cr
-CO
OMe
OMePh A OMe Ph

Ph
(CO)4Cr OMe OMe
Ph Ph
OMe Ph B C
Cr Ph Cr Ph
(OC)3 C (OC)3
O
O

OMe OMe OMe

Ph Ph Ph
Cr(CO)3 D Cr(CO)3 Cr(CO)3
C Ph Ph Ph
O H
O OH
 Dötz, K. H. Angew. Chem. Int. Ed. Engl. 1975, 14, 644.
Dötz reaction. A: Alkyne metathesis of Fischer carbene complex. B: Insertion of CO. C: Reductive
elimination to form a ketene. D: 6e Electrocyclic reaction.

B128
Et MgBr
Et Et Ti(Oi-Pr)2
i-PrO -EtH
Ti Oi-Pr)2
i-PrO ( H Ti(Oi-Pr)2 H Ti(Oi-Pr)2
A B C
Ti(Oi-Pr)2
Et MgBr

OMe
MeO
Me O O Me O OMe
Me Ti(Oi-Pr)2 Ti(Oi-Pr)2
Ti(Oi-Pr)2 D

MeO
Ti(Oi-Pr)2
Me O Me O Me OMgBr workup Me OH
OMe 2EtMgBr
Ti(Oi-Pr)2 E F +H+
+
Et
Ti(Oi-Pr)2
Et

Kulinkovich, O. G.; Sviridov, S. V.; Vasilevski, D. A. Synthesis 1991, 234.

Kulinkovich reaction. A: Substitution of the isopropoxide with EtMgBr. B: β-Elimination. C:
Reductive elimination to form a titanium ethylene complex (or a titanocyclopropane). D:
Carbotitanation. E.: Formation of a cyclopropane. F: Regeneration of the active reagent.