Tetracoordinate Boron Intermediates Enable Unconventional Transformations

Conspectus Organoboron compounds are a class of multifunctional reagents for the construction of carbon–carbon and carbon–heteroatom bonds in modern synthetic chemistry. The transformations of organoboron compounds are usually carried out through tetracoordinate boron intermediates and mainly include additions to unsaturated bonds, rearrangement reactions, transmetalation reactions, and so on. Although great progress has been achieved in improving tetracoordinate boron intermediates, there are still shortcomings, such as sparse activation modes, a paucity of reaction strategies and difficulties in stereoselective control. In this Account, we mainly discuss our recent advances in the development of unconventional transformations of organoboron compounds based on the design of tetracoordinate boron intermediates, including the following three topics: (1) the construction of C–B bonds; (2) the construction of C–C bonds; (3) the design and application of chiral tetracoordinate boron. The development of new strategies to build C–B bonds is of great interest for chemists. We have developed tandem reactions involving multiple tetracoordinate boron intermediates for the selective borylations of alkynes and the synthesis of stable tetracoordinate boron, including a domino-borylation-protodeboronation (DBP) strategy for selective borylations of alkynes, highly regio-, stereo-, and chemoselective Cu-catalyzed diborylation of β-CF 3 -1,3-enynes and cascade B–Cl/C–B cross-metathesis and C–H bond borylation for the synthesis of tetracoordinate triarylboranes. We have also developed novel strategies involving tetracoordinate boron intermediates to form C–C bonds because the formation of C–C bonds is an enduring theme of organic chemistry. We disclosed long distance or multiple migration reactions and novel coupling partners in transmetalation reactions, such as long distance 1,4-migrations of tetracoordinate nitrile oxide boron and nitrilium boron intermediates, multiple migrations of tetracoordinate isocyanide boron intermediate, palladium-catalyzed Suzuki–Miyaura coupling of thioureas or thioamides, copper-catalyzed atroposelective Michael-type addition, and a palladium-catalyzed atroposelective Catellani reaction. Moreover, in terms of stereoselective control of the tetracoordinate boron intermediate, we found that a chiral tricoordinate boron complex could activate water to form a chiral tetracoordinate boron complex with Brønsted acidity, which has been successfully applied with high enantioselectivity to the asymmetric catalytic reduction of challenging indoles. This Account summarizes our recent efforts using unconventional transformations of organoboron compounds for the design of tetracoordinate boron intermediates, which not only achieved the precise construction of a wide range of diverse C–B bonds and C–C bonds but also developed a novel chiral Brønsted acid for the asymmetric catalytic reduction of challenging indoles.