Borrowing Carbonate-Enabled Allylic Amination Reactions under Additive- and Reductant-Free Nickel Catalysis Employing Allylic Alcohols

A borrowing carbonate-enabled allylic cross-amination reactions employing allylic alcohol were discovered via merging acyl/allyl C-O bonds activation under nickel catalysis. The key component of this protocol is the ability of nickel [Ni(II)-Ni(0)] to execute a relay process via the nucleophilic trapping of the generated acyl Ni complex, resulting from the acyl C-O bond cleavage of dialkyl carbonates, followed by selective allylic C-O bond activations (allylic C-O vs alkyl C-O vs acyl C-O) to yield pi-allyINi-complexes. The finding truly represents Ni-catalyzed green allylic amination reactions under additive(s)-free conditions with excellent chemo- (N vs O), regio- (linear vs branched), and stereoselectivity (E vs Z) with a wide range of fundamentally challenging N-heterocycles and allylic alcohols. The reaction is scalable, does not require harmful reaction media and a globe box, and is successfully applied to the scale-up synthesis of pharmaceuticals (cinnarizine, flunarizine, and naftifine) with promising yields.

Automated summary

This translation discusses a method of synthesis using carbonate-enabled allylic cross-amination reactions under nickel catalysis, showing high selectivity and successful application in the Ni-catalyzed green allylic amination reactions to synthesize a range of organic compounds.