Electrophilic Amination of Diarylzincs and Triarylzincates with Acetone -(2,4,6-Trimethylphenylsulfonyl) Oxime and with O-Methylhydroxylamine

Selective Synthesis and Reactivity of η5‐Arylcyclohexadienyliron Complexes

“…IR (CH 3 CN): ñ max = 2105 (n sym CO), 2056 cm À1 (n asym CO); elemental analysis calcd (%) for C 16 H 13 F 6 FeO 4 P (470.08): C 40.9, H 2.8; found: C 40.6, H 2.6. (25): Following a modification of general method G, 4-bromoanisole (16.45 g, 879 mmol), magnesium turnings (2.14 g, 87.9 mmol), copper(I) iodide (trace), one small crystal of iodine, dry Et 2 O (100 mL) and zinc chloride (26.3 mL of 1.0 m solution in dry Et 2 O, 26.3 mmol) were used to prepare bis(4-methoxyphenyl)zinc [48] which separated as a lower, brown oil (nominally 26.3 mmol). A portion of this oil (14 mL) was reacted with the 2-methoxy salt (4, X= OMe) (4.10 g, 10.41 mmol) in THF (70 mL) to produce, after work-up [sat.…”

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.…”

Highly efficient catalytic system for electrophilic amination of arylzinc reagents

“…The reactivity of organozinc reagents can be increased by using transition metal catalysts. Even though copper catalysis has been known to promote the reactions of organozinc reagents, the amination reaction of ordinary organozinc reagents with oximes in the presence of copper catalyses was not effective enough to provide the preparation of primary aryl amines in high yields 7…”