Electrophilic amination of organozinc reagents with acetone O-(2,4,6-trimethylphenylsulfonyl)oxime and O-methylhydroxylamine

Abstract

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Nickel-Catalyzed Electrophilic Amination of Organozinc Halides

“…Reports by Erdik and Narasaka on the metal-catalyzed amination of nonstabilized carbanions employing O-sulfonyl oximes as H 2 N(+) synthons represent an improvement on previous methodology, but have as yet been limited to the preparation of non-functionalized aniline derivatives. 12,13 Rieke's observation that organozinc halide reagents undergo amination with azodicarboxylates is also germane to the present investigation. 14 In the course of our initial screen of potential catalysts and reagents for the union of weak organic nucleophiles with R 2 N(+) synthons, nickel arose as a candidate metal for the reaction of R¢ZnX with O-benzoyl hydroxylamines.…”

Competitive kinetic study of the amination of organomagnesium and -zinc reagents with acetoneO-sulfonyloxime

“…As model reactions, we chose amination of phenylmagnesium bromides in THF at reflux temperature and phenylzinc chlorides in the presence of CuCN catalysis in THF at room temperature. These conditions were already optimized in the synthetic investigation of the amination of arylmetals with 5f (metal: MgBr, 23 -25 ZnCl/'CuCN' 26,27 ). The effect of substituents were studied by collecting competitive rate data in the amination of phenylmetals and six of their 3-and 4-substituted derivatives, and looking for a Hammett correlation for the competitive rate ratios of phenylmetal-substituted phenylmetal pairs.…”

“…25 We also used 5f for amination of organozincs in the presence of CuCN catalysis at room temperature. 26,27 Ketone O-(arenesulfonyl)oximes (5) aminate carbanions, giving N-organylimines as isolable intermediates, which then hydrolyzed to imines (Scheme 4). 18,20,21 We are currently trying to provide kinetic supports for the possible mechanisms of electrophilic aminations of carbanions in a program of research.…”

Kinetic study of the amination of Grignard reagents and cuprates with O‐methylhydroxylamine

“…As source of the carbanions, we used Grignard reagents, stoichiometric bromomagnesium cuprates and catalytic zinc cyanocuprates (Scheme 3). The reaction temperatures for the amination of these organometallics with 1 were already optimized 16,21,22 as À15 to 0 C for organolithiums, Grignard reagents and bromomagnesium cuprates and room temperature for CuCN-catalyzed monoor diorganozinc reagents. Since Beak et al's results 10 on the reaction of organolithiums provided a reminder of the need for caution in the interpretation of results due to the composition of aggregates, we omitted the amination of organolithiums with 1 for competitive kinetics.…”