trans-Selective Element-Element′ Addition to Alkynes

The trans-addition of intermetallic sigma-bonds (E-E '; E E'=Si, B, Se, P, Sn, etc.) across alkynes has emerged as an exceptionally atom-economical means of constructing multi-substituted alkenes, which readily transform into densely functionalized and biologically active compounds. Compared to the widely studied cis-E-E' additions, trans-E-E' additions remain a more challenging and underdeveloped area. In this article, recent advances in trans-E-E' additions are summarized, encompassing various interelement compounds such as Si-Si, B-B, Si-B, P-B, Se-B, and B-Sn. We aim to provide a deeper understanding of trans-E-E' additions and facilitate the further development of synthetic methodologies and applications of vicinally trans-bismetallated alkenes.