Radical–nucleophilic substitution (S<sub>RN</sub>1) reactions: preparation and reactions of α-nitrosuiphides
作者:W. Russell Bowman、Geoffrey D. Richardson
DOI:10.1039/p19800001407
日期:——
α-Nitrosulphides were prepared by SRN1 reaction of 2-bromo-2-nitropropane with thiolate anions, and by SN2 attack of sodium 2-nitropropan-2-ide on symmetrical disulphides. The α-nitrosulphides undergo radicalnucleophilic substitution (SRN1) by nitronate, sulphinate, and malonate anions, but not by thiolate anions.
The use of tricyclohexylphosphine (and related phosphines) in palladium-catalysedallylicsubstitution reactions enables the selective conversion of branched allylic acetates into the branched substitution products (up to 120:1 regioselectivity). Linear allylic acetates do not show the same selectivity for the branched substitution products, thereby demonstrating a memory effect.
Novel radical chain substitution reaction involving single electron transfer SET processes
作者:Rui Tamura、Kunihiko Yamawaki、Nagao Azuma
DOI:10.1021/jo00020a004
日期:1991.9
Beta-Substituted alpha[(phenylsulfonyl)methyl]- and alpha-z[(phenylthio)methyl]cyclohexenones 1-4 underwent regioselective replacement of the sulfonyl and sulfenyl groups by stabilized carbanions such as LiCMe2NO2 mainly by a radical chain mechanism, which was confirmed by investigating the effects of photoirradiation, radical scavengers, and reaction solvents and by the ESR and spectroscopic studies.