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The data obtained by the authors in the field of chemistry of substituted borolanes and 2,3-dihydro-1H-boroles are summarized. The authors developed a selective method for the synthesis of five-membered boracarbocycles via transmetalation of aluminacarbocycles, obtained by catalytic cycloalumination of unsaturated compounds (terminal olefins or acetylenes) with AlEt3 in the presence of Cp2ZrCl2 as a catalyst, by boron halides (BF3·Et2O, BCl3, BBr3). Some examples of the use of this approach to modify steroid compounds (in particular, to introduce a borolan fragment into them) are described in this review.