Synthesis and Reactions of Functionally Substituted 2-(Adamantan-1-yl)oxiranes

Abstract

Functionally substituted oxiranes were synthesized by epoxidation of unsaturated compounds of the adamantane series with m-chloroperoxybenzoic acid. Adamantyl-substituted epibromohydrins reacted with nitrogen, oxygen, and sulfur nucleophiles to give only halogen substitution products. 2-(Adamantan-1-yl)-3-hydroxypropanoic acid was obtained by the reaction of 2-(adamantan-1-yl)-2-(bromomethyl)oxirane with 98% nitric acid. Acid-catalyzed ring opening of aminomethyloxiranes afforded trifunctional derivatives, adamantane-containing aminohalohydrins. Treatment oftrans-2-(adamantan-1-yl)-2-(phenylsulfanylmethyl)oxirane withn-butyllithium gave rise to a mixture ofZ and E isomers of 1-(adamantan-1-yl)-3-(phenylsulfanyl)prop-2-en-1-ol, whereas trans-2-(adamantan-1-yl)-3-(phenoxylmethyl)oxirane under similar conditions was converted to (E)-3-(adamantan-1-yl)prop-2-enal.