Recently, gem-diborylalkanes have attracted much attention as versatile building blocks and fundamental intermediates in organic synthesis, because they enable multiple C-C bond construction and further transformation at C-B bonds. Importantly, gem-diborylalkanes can be utilised as bisnucleophilic partners in a variety of chemo-selective C-C bond-forming reactions. This review describes recent developments in synthesising gem-diborylalkanes in complex molecules along with their chemical transformation. In the first part of the review the different synthetic approaches used to synthesise gem-diborylalkanes are described. In the second part, an overview of the chemoselective transformation of gem-diborylalkanes into various functionalized materials is discussed along with one-carbon homologation of diborylmethane via a selective uni- and bidirectional method.

A ruthenium-catalyzed chelation-assisted C-H bond activation of aromatic ketones and the reaction with olefins to provide Heck-type products in good to excellent yields with a high regio- and stereoselective manner is described.

Various aromatic and heteroaromatic aldehydes reacted with activated alkenes in the presence of a catalytic amount of [{RuCl(2)(p-cymene)}(2)], AgSbF(6), and Cu(OAc)(2)·H(2)O to give substituted alkene derivatives in a highly regio- and stereoselective manner. The corresponding alkene derivatives were further converted into unusual four-membered cyclic ketones or a polycyclic isochromanone derivative via a photochemical rearrangement. Notably, the catalytic reaction was conducted under an open atmosphere.

A ruthenium-catalyzed oxidative coupling of substituted aromatic and heteroaromatic esters with alkenes in the presence of catalytic amounts of AgSbF(6) and Cu(OAc)(2) to provide highly substituted alkene derivatives in good to excellent yields under an open atmosphere is described.