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Rhodium-Catalyzed 1,4-Aryl Rearrangement of Sulfur Ylide for the Synthesis of 2-Pyridyl Thioethers

Jie Wang, Qingyang Li, Shanshan Wang, Xin‐Yan Wu, Xingguang Li, Pei Nian Liu

2023Organic Letters12 citationsDOI

Abstract

We report a novel rhodium-catalyzed rearrangement involving N-substituted 2-thiopyridones and diazoesters. This reaction proceeds through the rhodium-catalyzed formation of sulfur ylides, followed by a direct C-N bond cleavage to achieve N-to-C 1,4-pyridyl migration. The protocol can be used to construct various thiopyridines possessing tetrasubstituted carbon stereocenters in moderate to excellent yields, which expands the transformation pattern of sulfur ylide intermediates in rearrangement reactions.

Topics & Concepts

YlideChemistryRhodiumStereocenterArylCatalysisSulfurMedicinal chemistryBond cleavageCleavage (geology)Organic chemistryEnantioselective synthesisAlkylGeotechnical engineeringEngineeringFracture (geology)Cyclopropane Reaction MechanismsSulfur-Based Synthesis TechniquesCatalytic C–H Functionalization Methods
Rhodium-Catalyzed 1,4-Aryl Rearrangement of Sulfur Ylide for the Synthesis of 2-Pyridyl Thioethers | Litcius