Convergent Approach for the Asymmetric Synthesis of Vinyl Sulfoximines via Ruthenium-Catalyzed Enantioselective Alkylation of Sulfenamides with (Diazomethyl)phosphonates

The Ru(II)-(S)-tBu-Pheox-catalyzed enantioselective alkylation of sulfenamides with (diazomethyl)phosphonates proceeds in high yields typically with >90:10 er and at ≤1 mol % catalyst loading. A broad sulfenamide scope was observed, including (hetero)aryl S substituents with different steric and electronic characteristics as well as S-alkyl groups with different steric properties. Oxidation followed by the Horner–Wadsworth–Emmons reaction under mild conditions provides vinyl sulfoximines as exemplified by the asymmetric syntheses of sulfoximine analogues of two vinyl sulfone clinical candidates, K777 and recilisib.