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.
Reported is the first enantioselective oxidative Pummerer-type transformation using phase-transfer catalysis to deliver enantioenriched n class="Chemical">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.
Authors: Yernaidu Reddi; Cheng-Che Tsai; Carolina M Avila; F Dean Toste; Raghavan B Sunoj Journal: J Am Chem Soc Date: 2018-12-28 Impact factor: 15.419
Authors: Banruo Huang; Ying He; Mark D Levin; Jaime A S Coelho; Robert G Bergman; F Dean Toste Journal: Adv Synth Catal Date: 2019-09-06 Impact factor: 5.837
Authors: Jaime A S Coelho; Akira Matsumoto; Manuel Orlandi; Margaret J Hilton; Matthew S Sigman; F Dean Toste Journal: Chem Sci Date: 2018-08-03 Impact factor: 9.825