SMALL-RING COMPOUNDS. XXVIII. ISOTOPE-POSITION REARRANGEMENTS OF ALLYLCARBINYL GRIGNARD REAGENTS¹

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

“…Then methoxyamine was used by several research groups for the electrophilic amination of various organomagnesium compounds. [30][31][32] Reaction of alkylmagnesium reagents with LiNHOCH 3 was found to be unsuccessful. 33,34 Preparation of aniline by the electrophilic amination of phenylmagnesium bromide using Ophenylhydroxylamine as aminating reagent was achieved in high yield.…”

Carbanions. 17. Rearrangements of 2,2-diphenyl-4-pentenyl alkali metal compounds

“…4.4-Diphenyl-l-butene was prepared by reaction of diphenylmethylpotassium in liquid ammonia-ether with allyl chloride by a method similar to that of Kuznetsov and Libman.11 The product after distillation in vacuo was obtained in 87% yield of product of bp 115 °C (2 Torr); n20D 1.5704 [lit.11 bp 114-116 °C (2 Torr); n20D 1.5715)]; NMR (neat) 7.2 (10 H, m), 5.65 (1 H, m), 5.00 (2 H, m), 4.00(1 H, t, J = 8 Hz), and 2.75 (2 H, t, J = 8 Hz).…”

“…In initial experiments the distribution of carbon-14 was determined by ozonization and assay of radioactivity in the dimethone derivative of the resulting formaldehyde, according to a general procedure which gave satisfactory results with simple aliphatic compounds.13•14 A check with the milder oxidizing system sodium periodate-osmium tetroxide,15 however, the assumption that the allyl group in the rearranged organolithium compound 4 (and in the acid 7 derived by carbo-Journal of the American Chemical Society / 99:6 / nation) should have the same activity as that of the allyllithium prevailing in the solution at the time of its formation, the activity of the rearranged acid 7 is calculated176 to be 0.188 ¿iCi/mmol; the observed activity, however, is only 14% of this calculated value or 13% of that of the final allyllithium.…”

Transition Metal-Catalyzed Reactions of Methylenecyclopropanes

“…[41] The distal bond cleavage of 106 would afford the pallylpalladium intermediate 107, leading to 102 and Pd(0) upon reductive coupling. The proximal bond cleavage of 108 would give homoallylpalladium 109, [61] which would undergo migration to p-allylpalladium 110, [6] and subsequent reductive coupling would produce 103 and Pd(0).…”