Reactivity of mixed organozinc and organocopper reagents. 3. Atom economic electrophilic amination of methyl arylzinc reagents

Abstract

Reaction of methyl arylzincs with acetone O-(mesitylenesulfonyl)oxime in THF in the presence of CuCN at room temperature is efficient in selective electrophilic amination of aryl carbanions. This procedure allows for the preparation of arylamines in moderate to good yields and provides an efficient and atom economic alternative to existing amination methods for diarylzincs.

Synthesis of amines by the electrophilic amination of organomagnesium, -zinc, -copper, and -lithium reagents

“…102 Dialkylzinc reagents react with imino esters to give the N-alkylation product as the major product or the only product, whereas alkylzinc and benzylzinc halides react to give the carbophilic addition product. 48,[103][104][105] Diethylzinc reacts with α-ketimino esters 16a-d in toluene at room temperature to produce Nethylation products in high yields (Scheme 27).…”

Reactivity of mixed organozinc and mixed organocopper reagents: 14. Phosphine-nickel catalyzed aryl-allyl coupling of (n-butyl)(aryl)zincs. Ligand and substrate control on the group selectivity and regioselectivity

“…Theoretical studies on the control of group selectivity have been reported by Nakamura [32,33] and experimental studies on the effects of organyl groups on the reactivity and selectivity of mixed cuprates have been reported by Bertz [34] and Nakamura [35]. Our group carried out a series of synthetic and mechanistic work [36e40] on the reactivity and group selectivity of mixed diorganozincs, R 1 R 2 Zn [36]; mixed diorganocuprates, R 1 R 2 CuM (M ¼ MgBr [37], ZnCl [38]) and Cu catalyzed mixed triorganozincates, R 1 (R 2 ) 2 ZnMgBr [38] in their CeC [36], C-COR [39], C-COOR [38] and CeN coupling [40] reactions. We showed that the group selectivity of both mixed diorganocuprates and diorganozincs can be controlled by changing reaction parameters, i.e.…”

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

“…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 connection with my recent studies on the control of group selectivity in acylation of n ‐alkylphenylzinc reagents and kinetics of acylation of iodozinc alkylarylcuprates, I focused my interest on the acylation of n ‐alkylarylzinc reagents with the objectives of kinetics and mechanism of phosphine‐catalyzed acylation of diorganozincs and providing another kinetic support for Erdik's hypothesis regarding the dependence of R T group transfer ability on R R group in reactions of R R R T Zn reagents. According to the best of my knowledge, there is a limited number of reported work on the kinetics of reactions of uncatalyzed and Cu(I)‐ and Ni(II)‐catalyzed reactions of monoorganozincs and diorganozincs. A theoretical study for transfer ability in mixed diorganozincs has been also published .…”