ORGANOBORANES FOR SYNTHESIS .17. GENERALITY OF HYDROBORATION-AMINATION FOR THE CONVERSION OF TERPENES INTO ENANTIOMERICALLY PURE TERPENYLAMINES - THEIR UTILITY FOR GAS-CHROMATOGRAPHIC ANALYSIS OF CHIRAL CARBOXYLIC-ACIDS

The generality of our new convenient synthesis of isopinocampheylamine s by hydroboration-amination of alpha-pinene has been established by c onverting representative terpenes into optically pure terpenylamines, such as (-)-cis-caran-trans-2-amine, (-)-cis-caran-trans-4-amine, (-)- longifolamine, and (+)-cis-myrtanylamine. The synthesis involves conve rting the terpene into the B-chloroditerpenylborane by treatment with chloroborane-methyl sulfide. This is treated with trimethylaluminum to form the B-methylditerpenylborane, and the latter is converted into t he amine by treatment with hydroxylamine-O-sulfonic acid. cis-Myrtanyl amine has been shown to be as effective as isopinocampheylamine far th e gas chromatographic analysis of racemic carboxylic acids as their di astereomeric amides, suggesting the generality of this application of terpenylamines as chiral derivatizing agents. Copyright (C) 1996 Elsev ier Science Ltd.