Stereospecific C–O sulfation via persulfate-induced 1,4-metallate migration

Abstract

Sulfation, a ubiquitous post-translational modification in biomolecules, primarily targets substrates containing OH groups through O-sulfonation (O–SO3). A method for sulfation via the formation of C–O bonds has the potential to access organic sulfates from a broad substrate scope and in a stereoselective manner but remains elusive. Stereospecific C–O bond formation via 1,2-metallate migration in peroxide oxidation has not been deployed to create any other valuable C–O bonds apart from C–OH. Here we describe a fundamentally unique reactivity of persulfate salts for stereospecific C–O sulfation via 1,4-metallate migration. With the aid of readily accessible, stereodefined organic boron compounds derived from native functionalities and a tandem borylation–sulfation approach, our study thus expands to include hydrosulfation of alkenes, C–H sulfation, decarboxylative sulfation, dehalogenative sulfation and deaminative sulfation, which are not otherwise readily accessible. O-sulfonation is a common method for producing organosulfates but is limited to hydroxyl compounds. Here the unique reactivity of persulfates enables stereospecific C–O sulfation via 1,4-metallate migration. This approach provides an unprecedented platform to readily access structurally diverse organosulfates from a wide substrate scope.