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 otherO-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.