Reactivity of mixed organozinc and mixed organocopper reagents: 5-A kinetic insight to compare the transfer ability of the same group in copper catalyzed alkylation of mixed and homozincates

Reactivities of mixed organozinc and mixed organocopper reagents. Part 13 Kinetic study for phosphine‐catalyzed acylation of alkylarylzincs and effect of residual group on the transfer rate of alkyl group

“…For the evaluation of the rate data, I used the method that we already successfully used in the kinetics work of stoichiometric mixed cuprates, R 1 R 2 CuMgBr and R 1 R 2 CuZnI, catalytic mixed cuprates, and also mixed diorganozincs, R 1 R 2 Zn . In applying this method for concentration of electrophilic partner at time t , calculated value was used rather than directly measured value and it was calculated as c = [Electrophile] t = [Electrophile] 0 − ∑[Product] t .…”

“…In their systematic work, Erdik and coworkers observed that the group selectivities of mixed diorganocuprates, R 1 R 2 CuM (MMgBr), ZnI, diorganozincs, R 1 R 2 Zn, and Cu‐catalyzed mixed triorganozincates, R 1 (R 2 ) 2 ZnMgBr, depend on the reaction parameters, that is, the electrophilic substrate, the solvent, and the temperature as well as the transition metal catalyst and organocatalyst, and reported that the group selectivity of mixed organocopper and organozinc reagents can be controlled by changing the reaction parameters. They also developed new atom‐economic synthetic procedures for CC, C‐acyl, and CN coupling employing mixed arylzinc reagents. However, probing the origin of group selectivity in the mixed organocopper and organozinc reagents still seems a problem.…”

“…In addition, alkylation rate of n ‐Bu group in n ‐Bu(FGC 6 H 4 )CuMgBr reagents and acylation rate of n ‐Bu group in n ‐Bu(FGC 6 H 4 )CuZnI reagents change depending on FG substituents. However, alkylation rate of Ph group in catalytic n ‐BuPhCuMgBr, which is derived from n ‐BuPh 2 ZnMgBr and CuI catalyst, was found higher than that of catalytic homocuprate Ph 2 CuMgBr . They also compared the reaction rate of transferable Ph group in allylation of ( n ‐alkyl)PhZn reagents and found that it changes depending on n ‐alkyl group, and all higher than that in Ph 2 Zn…”

Reactivity of mixed organozinc and mixed organocopper reagents: 11. Nickel‐catalyzed atom‐economic aryl–allyl coupling of mixed (n‐alkyl)(aryl)zincs

“…However, Erdik and co‐workers in their serial work on the reactivity and group selectivity of mixed organometallics reported that the group selectivity of mixed diorganozincs R 1 R 2 Zn, mixed diorganocuprates R 1 R 2 CuM (M = MgBr, ZnCl) and Cu‐catalyzed mixed triorganozincates R 1 (R 2 ) 2 ZnMgBr depends on the reaction parameters, such as solvent and catalyst. They also developed new atom‐economic procedures for C–alkyl, C–N and C–acyl coupling reactions using mixed diorganozincs R R R T Zn.…”

Reactivities of mixed organozinc and mixed organocopper reagents. Part 7. Comparison of the transfer rate of the same group in allylation of mixed and homo diorganozinc reagents

“…During our continuing work on the reactivity and controlling factors of the group selectivity of mixed diorganozinc reagents, R 1 R 2 Zn, mixed diorganocuprate reagents, R 1 R 2 CuM (M = MgBr, ZnCl) and mixed triorganozincate reagents, R 1 (R 2 ) 2 ZnMgBr, we observed that the group selectivity of R 1 R 2 Zn reagents depends on the reaction parameters, i.e. the electrophilic substrate, the solvent and the temperature as well as the transition metal catalyst and/or organocatalyst.…”