Litcius/Paper detail

Enantioselective Inter- and Intramolecular Sulfenofunctionalization of Unactivated Cyclic and (<i>Z</i>)-Alkenes

Anastassia Matviitsuk, Jesse L. Panger, Scott E. Denmark

2022ACS Catalysis21 citationsDOIOpen Access PDF

Abstract

A method for the enantioselective, Lewis base-catalyzed sulfenofunctionalization of cyclic and (Z)-alkenes is reported. The intermediate thiiranium ion generated in the presence of a selenophosphoramide catalyst is intercepted by a variety of nucleophiles. A diverse array of inter- and intramolecular functionalizations proceed in high yield and good to high enantioselectivity (86:14–98:2 er). Prior experimental and computational studies indicated such enantiotopic face discrimination to be poor; however, the results disclosed herein remediate the previous findings. Control experiments were performed to investigate the different behavior of (Z)-alkenes and their more established (E)-counterparts.

Topics & Concepts

Enantioselective synthesisIntramolecular forceNucleophileYield (engineering)ChemistryCatalysisLewis acids and basesCombinatorial chemistryStereochemistryMedicinal chemistryComputational chemistryOrganic chemistryMaterials scienceMetallurgySulfur-Based Synthesis TechniquesVanadium and Halogenation ChemistryChemical Synthesis and Reactions