Bis(pinacolato)diboron‐Enabled Ni‐Catalyzed Reductive Arylation/Vinylation of Alkyl Electrophiles

Abstract Herein, the use of economically and environmentally friendly bis(pinacolato)diboron (B 2 Pin 2 ) is described as a non‐metallic reductant in mediating Ni‐catalyzed C(sp 3 )–C(sp 2 ) reductive cross‐coupling of alkyl electrophiles with aryl/vinyl halides. This method exhibits excellent suitability for heteroaryl halides and alkyl halides/Katritzky salts. The present study is compatible with an in situ halogenation of alcohol method, allowing for selective mono‐functionalization of diols and bio‐relevant alcohols (e.g., carbohydrates). The use of B 2 Pin 2 shows potential for easy scalability without introducing additional metal impurities into the products. It is observed for the first time in the realm of cross‐electrophile coupling chemistry that B 2 Pin 2 can sever as a reductant to reduce Ni II to Ni 0 . This mechanistic insight may inspire the development of new reductive bond‐forming methodologies that can otherwise be difficult to achieve with a metal reductant.