Unsymmetrical 1,1-bis(boryl)alkanes and alkenes are organo-bismetallic equivalents, which are synthetically important because they allow for sequential selective transformations of C–B bonds. We reviewed the synthesis and chemical reactivity of 1,1-bis(boryl)alkanes and alkenes to provide information for the synthetic community. In the first part of this review, we disclose the synthesis and chemical reactivity of unsymmetrical 1,1-bisborylalkanes. In the second part, we describe the synthesis and chemical reactivity of unsymmetrical 1,1-bis(boryl)alkenes.

Organophosphonium salts containing C(sp 3 ) À + P bonds are among the most utilized reagents in organic synthesis for constructing CÀCd ouble bonds.H owever,t heir use as C-selective electrophilic groups is rare.Here,weexplore an efficient and general transition-metal-free method for sequential chemo-and regioselective C À Ha nd C(sp 3 ) À + P bond functionalizations.I nt he present study,C À Ha lkylation resulting in the synthesis of benzhydryl triarylphosphonium salts was achieved by one-pot, four-component cross-coupling reactions of simple and commercially available starting materials.T he utility of the resulting phosphonium salt building blocks was demonstrated by the chemoselective post-functionalization of benzylic C(sp 3 ) À + PPh 3 groups to achieve aminations,t hiolations,a nd arylations.I nt his way, benzhydrylamines,benzhydrylthioethers,and triarylmethanes, structural motifs that are present in many pharmaceuticals and agrochemicals,a re readily accessed. These include the synthesis of two anticancer agents from simple materials in only two to three steps.A dditionally,aprotocol for late-stage functionalization of bioactive drugs has been developed using benzhydrylphosphonium salts.T his new approach should providenovel transformations for application in both academic and pharmaceutical research.