Zhang, GuotingCramer, Nicolai2023-04-102023-04-102023-04-102023-03-1510.1002/anie.202301076https://infoscience.epfl.ch/handle/20.500.14299/196751WOS:0009492914000011,3,2-diazaphospholene hydrides (DAP-H) enable smooth conjugate reduction of polarized double bonds. The transiently formed phosphorus-enolate provides a potential platform for reductive alpha-functionalizations. In this respect, asymmetric C-heteroatom bond forming processes are synthetically appealing but remain elusive. We report a 1,3,2-diazaphospholene-catalyzed three-step cascade reaction of N-sulfinyl acrylamides comprised of conjugate reduction, [2,3]-sigmatropic aza-Mislow-Evans rearrangement and subsequent S-O bond cleavage. The obtained enantio-enriched alpha-hydroxy amides are formed in good yields and excellent enantiospecificity. The stereo-defined P-bound N,O-ketene aminal ensures an excellent transfer of chirality from the sulfur stereocenter to alpha-carbon. The transformation operates under mild conditions at ambient temperature. Moreover, DAP-H is a competent reductant for the cleavage of formed sulfenate ester, eliminating the extra step in traditional Mislow-Evans processes.Chemistry, MultidisciplinaryChemistryasymmetric synthesisdiazaphospholenesmain group catalysisphosphoroussigmatropic rearrangementmain-group elementsallylic sulfoxidesefficient synthesishydroxy amidesalpha-hydroxyhydroborationinterconversionreactivitymechanismumpolungtext::journal::journal article::research article