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Reactivity of mixed organozinc and mixed organocopper reagents. Part 4: a kinetic study of group transfer selectivity in CC coupling of mixed diorganocuprates
Author(s) -
Erdik Ender,
Özkan Duygu
Publication year - 2009
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1567
Subject(s) - chemistry , reagent , electrophile , reactivity (psychology) , nucleophile , alkyl , medicinal chemistry , cuprate , group (periodic table) , selectivity , leaving group , copper , transfer (computing) , computational chemistry , organic chemistry , catalysis , medicine , physics , alternative medicine , optoelectronics , pathology , doping , parallel computing , computer science
The competitive rate data and Taft relationships for the coupling of bromomagnesium n ‐butyl (substituted phenyl) cuprates with alkyl bromides show that selective n ‐butyl transfer can be explained by an oxidative addition mechanism. Taft reaction constants also show that the residual group FG‐C 6 H 4 in the mixed cuprate n ‐Bu(FG‐C 6 H 4 )CuMgBr changes the ability of the copper nucleophile to react with the electrophile RBr. These results provide support for the commonly accepted hypothesis regarding the dependence of the R 1 group transfer ability on the strength of R 2 Cu bond in reactions of R 1 R 2 CuMgBr reagents. Copyright © 2009 John Wiley & Sons, Ltd.