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Enantioselective Synthesis of N , S ‐Acetals by an Oxidative Pummerer‐Type Transformation using Phase‐Transfer Catalysis
Author(s) -
Biswas Souvagya,
Kubota Koji,
Orlandi Manuel,
Turberg Mathias,
Miles Dillon H.,
Sigman Matthew S.,
Toste F. Dean
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201711277
Subject(s) - enantioselective synthesis , intramolecular force , chemistry , catalysis , nucleophile , sulfur , transition state , substrate (aquarium) , computational chemistry , combinatorial chemistry , organic chemistry , stereochemistry , oceanography , geology
Reported is the first enantioselective oxidative Pummerer‐type transformation using phase‐transfer catalysis to deliver enantioenriched sulfur‐bearing heterocycles. This reaction includes the direct oxidation of sulfides to a thionium intermediate, followed by an asymmetric intramolecular nucleophilic addition to form chiral cyclic N , S ‐acetals with moderate to high enantioselectivites. Deuterium‐labelling experiments were performed to identify the stereodiscrimination step of this process. Further analysis of the reaction transition states, by means of multidimensional correlations and DFT calculations, highlight the existence of a set of weak noncovalent interactions between the catalyst and substrate that govern the enantioselectivity of the reaction.