The Synthesis of Chiral Allyl Carbamates via Merger of Photoredox and Nickel Catalysis

A mild, and versatile, organophotoredox/Ni‐mediated protocol was developed for the direct preparation of diverse, enantioenriched allyl carbamates. The reported approach represents a significant departure from classical step‐by‐step synthesis of allyl carbamates. This dual photoredox/Ni based strategy offers unrivalled capacity for convergent unification of readily available alkyl halides and chiral carbamates derived from 1‐bromo‐alken‐3‐ols with high chemoselectivity and efficiency. The reported photoredox/Ni catalyzed cross‐coupling reaction is not limited to carbamates, but also to other O‐derivatives such as esters, ethers, acetals, carbonates or silyl ethers. To demonstrate the utility of the reported protocol, the resulting allyl carbamates were transformed into functionalized non‐racemic allylamines through a sigmatropic rearrangement reaction in enantiospecific manner. This approach allowed for synthesis of enantiomeric allylamines by a simple control of the geometry of a double bond of allyl carbamates.