Organic Reaction Mechanisms 1997

2BuLi + CuI

BuLi + BuCu + LiI

toluene

Et2O

O

LiX

O

Bu2CuII

·Et2O

Bu2CuLi · OEt2 + LiI · OEt2

					O–Li+
	O–Li+
Bu	Cu				Bu
EtO
	Bu

(153)

SCHEME 31

J

OPiv

PivO O

PivO

Ph

N

O

O O

(154)

OPiv

			PivO						O
			PivO
1. Et2AlCl
			X
2. NXS		Ph							O
					N
			Et O			O
			(155) de = 91:6:3

$ $ $ $ $

$

O					O			O
C6H13-C ≡ CH +			+ H2O	CpRu(Cl)COD
					C6H13

SCHEME 32

						COR3		COR3
			COR3	base			+
LnM+	R1	+ R2			R2	R1	R1	R2
	Br–
(156a) M = Te			(157)			(158)		(159)
(156b) M = As					M = Te > 85:15

M = As < 10:90

M#

J

M

M

M

M

J

O						N
Ph					Ar	N

(161)

O (160)

O

Ph Ar

O– N

N :

O–

Ph Ar

O N

N+

O–

Ph Ar

ON

+

N

O

Ph Ar

O– N

+

N

O–

Ph Ar

ON

N+

SCHEME 33

O

Ph Ar

N

O

(162) N

O–

PhO

H

O–

O2N

N+

PhOH

O2N

N+

O

O

N

N

O2N

–O2N

(163)

(164)

OH

HO

O–

O–

O2N

N

+

+ O

N

N

+

2

O

O

N

N

–O2N

–O2N

(165)

(166)

SCHEME 34

O

O

O

Cl

SMe

H

Cl

SMe

MeSNa

SMe

SMe

Cl

Cl

MeS

O

O

O

MeS–

(167)

(168)

)

^

^

^ ^

^ ^ ^ ^- ^

!

]

Organic Reaction Mechanisms, 1997 An Annual Survey Covering the Literature Dated December 1996 to November 1997 Edited by A.C. Knipe and W.E. Watts Copyright © 2001 John Wiley & Sons, Ltd

ISBNs: 0-471-89935-6 (Hardback); 0-470-84580-5 (Electronic)

#

#

#

# # # #

$ $ ! " $ $

# # #

# # # # #

#

#

M #

#

K K

O

O

OMe

OMe

Ph

O

hν

Ph

O

OO

OO Me Me

Ph

O

–60 °C, 60 h,

O

OMe

C6H5Me

Ph

OMe

O

O

(1)

LiAlH4, THF

Ph

PPh2

Ph

OH

Ph

PPh2

Ph

OH

(2)

80%

SCHEME 1

# #

#

O

O

O

H

O

O

MeONa/

hν

O

MeOH

67%

O

CH2Cl2, rt

R

O

O

H

O

O

O

R

O

(3)

(4)

R = H, Me

SCHEME 2

#

#

#

#

#

#

#

#

K # #

H

SiMe3

SiMe3

O

O

H

H

O

C

Bu4NF/MeCO2H

hν

cyclohexane

THF

O

O

O

(5)

(6)

86%

(7)

70%

SCHEME 3

O

PhCH2CONH

PhCH2CONH

O

S

SiMe3

S

O

SiMe3

N

Pri2NEt, CH2Cl2

N

O

OTf

CO2-pMB

CO2-pMB

(8)

(9)

		O	H
	PhCH2CONH	S				SiMe3

N O

CO2-pMB 69%

SCHEME 4

J

#