Synthesis of C2B3 X-Heterocycles (X = C, N, P, O, S) from 1,3,5-Triborapentanes

The hydroboration of acetylene with HBCl2 yields the products (Cl2B)2CHMe (1a), (Cl2BCHMe)2BCl (2a), (Cl2BCHMeBCl)2CHMe (3a), and (ClBCHMe)3 (4a). The crystal structure of 4a as well as of the pentaiodo derivative 2b were determined. A mechanism for the formation of the different hydroboration products is proposed. The 1,3,5-triborapentane 2a serves as precursor for the synthesis of derivatives of 1,3,5-triboracyclohexanes, 1,3,5-tribora-2-aza-cyclohexanes, 1,3,5-tribora-2-phospha-cyclo-hexanes, and 1,3,5-tribora-2-thia-cyclohexanes. Their constitutions have been derived from spectroscopic studies. The crystal structure of the 1,3,5-tribora-2-oxa-cyclohexane derivative was also determined.