Reactions involving electron transfer. 9. Reaction of lithium dimethylcuprate with alkyl aryl ketones

Utilization of 1,1-dimethyl-4,6-di-tert-butylspiro[2,5]octa-3,6-dien-5-one as a ‘hypersensitive’ probe for single electron transfer to carbonyl compounds

“…We have found that the radical anion generated from 1,l-dime thyl-4,6-di-tert-but ylspiro [ 2,5 ]octa-3,6-dien-5-one 1 undergoes facile ring opening to the tertiary distonic radical anion at a rate constant estimated to be b 107 s-l (Scheme 1). 1 In this paper, we illustrate the use of this compound as a 'hypersensitive' probe for single electron transfer to carbonyl compounds from several nucleophiles.…”

“…The importance of electron transfer in the reactions of dialkyllithium cuprates with aromatic and a$-unsaturated carbonyl compounds is generally recognized .698- 19 House has suggested that substrates whose reduction potentials lie in the range of -1.4 to -2.35 V (vs. SCE), react with dimethyllithium cuprate via SET. 5 Based upon the estimated reduction potential of 1 (-2.5 V vs. 0.1 mol dm-3 Ag+/Ag == -2.2 V vs. SCE),' reaction of this substrate with MezCuLi should proceed via SET.…”

Surface photochemistry: the photolysis of α-methoxy acetophenones on silica gel

“…Compound l a was obtained commercially (Aldrich, 95%) and purified to -99% purity by fractional distillation. Compounds 1 b (28) and l c (29) were prepared by the reaction of 2-methoxypropionitrile (28) and 2-methoxyisobutyronitrile (30), respectively, with phenylmagnesium bromide. Compounds Id and l e were prepared by the method of Fisher (31) and Heine (32), respectively.…”

Reactions with Aziridines, XXXII[1]. Mechanistic Aspects in Nucleophilic Opening of Three‐Membered Rings. Alcoholyses of Activated Aziridines

“…The recently described multistep SET mechanism [27] of aziridine ring opening will also be influenced by other factors, particularly by the stability and rate of formation of the intermediate radical anion. The same type of SET mechanism has been discussed for acyl cyclopropanes by House [23] who, however, found the results of the reactions with dialkylcuprates incompatible with this mechanism.…”

“…The necessary water was introduced with the acid. The other by products, 2-oxazolines 12 (runs [14][15][16][17][18] and methallylamine Bf (runs [21][22][23][24][25], originate from branches of the SN I path. The acid catalyzed isomerization of N-acylaziridines to oxazolines [27] was shown to be consistent with a carbenium intermediate when stabilized by structure or solvent [28J.…”