A method for electrophilic sulfenylation by organophosphorus‐catalyzed deoxygenative O‐atom transfer from sulfonyl chlorides is reported. This C−S bond‐forming reaction is catalyzed by a readily available small‐ring phosphine (phosphetane) in conjunction with a hydrosilane terminal reductant to afford a general entry to sulfenyl electrophiles, including valuable trifluoromethyl, perfluoroalkyl, and heteroaryl derivatives that are otherwise difficult to access. Mechanistic investigations indicate that the twofold deoxygenation of the sulfonyl substrate proceeds by the intervention of an off‐cycle resting state thiophosphonium ion. The catalytic method represents an operationally simple protocol using a stable phosphine oxide as a precatalyst and exhibits broad functional‐group tolerance.

Sulfones are excellent candidates for the design of new C–C and C–X bond-forming reactions owing to the easy activation of C–S bonds. This review focuses on challenges and recent opportunities for catalytic functionalization of sulfones.

A preliminary mechanistic approach to the Cu-catalyzed carboboration of alkynes using B2(pin)2 was used as a blueprint for the rational design and development of a regiocontrolled, stereoselective carboboration of internal alkynes by reaction with a β,β-disubstituted acrylate fragment to provide synthetically versatile and densely functionalized pyrrolidines. Experimental observations and computational analysis relevant to understanding the activation role of the alkoxide functionality in this type of carboboration process were instrumental in developing a synthetic method broad in scope and functional group tolerance. Compounds obtained by this strategy feature a stereochemically defined tetrasubstituted vinyl boronate, together with an all-carbon quaternary stereocenter. This procedure involves a tandem regioselective, chemoselective, and diastereoselective borylcupration of unsymmetrical dialkyl alkynes, followed by migratory insertion of an activated olefin to a C–Cu bond.

A method for the annulation of amines and carboxylic acids to form pharmaceutically relevant azaheterocycles via organophosphorus P III /P V redox catalysis is reported. The method employs a phosphetane catalyst together with a mild bromenium oxidant and terminal hydrosilane reductant to drive successive C–N and C–C bond-forming dehydration events via the serial action of a catalytic bromophosphonium intermediate. These results demonstrate the capacity of P III /P V redox catalysis to enable iterative redox-neutral transformations in complement to the common reductive driving force of the P III /P V couple.