Sulphone-based elimination reactions in synthesis. Part 2. Diumycinol

Abstract

Diumycinol [2(Z), 6(E)-12-(2-methylene-6,6-dimethyl-1-cyclohexyl)-11-methylene-3,8,8-trimethyldodeca-2,6-dien-1-ol], a hydrolytic product of the antibiotic diumycin, was assembled from three fragments: 1-(2-phenylsulphonylethyl)-2-methylene-6,6-dimethylcyclohexane (28), 3-(2-iodoethyl)-3-methyloxetane (39), and (Z)-1-benzyloxy-6-phenylsulphonyl-3-methylhex-2-ene (3). An efficient synthesis of 2-methylene-6,6-dimethylcyclohexylmethanol (15)(γ-cyclogeraniol) was accomplished by a [2,3]sigmatropic rearrangement of 3,3-dimethylcyclohex-1-enylmethoxymethyl-lithium (17).