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Rh II ‐Catalyzed Reaction of α‐Diazocarbonyl Compounds Bearing β‐Trichloroacetylamino Substituent: CH Insertion versus 1,2‐H Shift
Author(s) -
Zhang Zhenhua,
Shi Weifeng,
Zhang Jian,
Zhang Bo,
Liu Bingge,
Liu Yiyang,
Fan Bo,
Xiao Fengping,
Xu Feng,
Wang Jianbo
Publication year - 2010
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200900352
Subject(s) - substituent , carbene , chemistry , migratory insertion , insertion reaction , steric effects , stereochemistry , stereoselectivity , catalysis , hydride , medicinal chemistry , organic chemistry , hydrogen
The Rh II ‐carbene reaction is dramatically affected by the neighboring substituents. If the neighboring substituent is an OH group, a1,2‐H shift is the exclusive pathway. If it is an OAc group, a 1,2‐acetoxy migration is observed. If it is p ‐toluenesulfonyl group, 1,3 and 1,5‐CH insertion are the major pathways, and the 1,2‐H shift is completely suppressed. If the adjacent substituent is a trichloroacetyl amino group, 1,5‐CH insertion competes with the 1,2‐hydride shift, and no 1,3‐CH insertion can be observed. Both electronic and steric factors are responsible for the switching of the Rh II ‐carbene reaction pathway. The highly stereoselective 1,5‐CH insertions in Rh II ‐catalyzed reaction of α‐diazocarbonyl compounds, bearing β‐trichloroacetylamino substituent, can be utilized as a novel way to synthesize five‐membered cyclic β‐amino acid derivatives.