Iron-catalyzed Fluoroalkylative Alkylsulfonylation of Alkenes Via Radical-anion Relay

Overview

Journal Nat Commun

Specialty Biology

Date 2024 Feb 17

PMID 38368406

Authors

Xiaoya Hou

Hongchi Liu

Hanmin Huang

Affiliations

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Abstract

Transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts of metal reductant and the requirement of installing a directing group into alkenes to suppress the inherent β-H elimination bring great limitations to this type of reaction. We demonstrate herein that the difunctionalization of alkenes with two different alkyl halides is accessible via a radical-anion relay with NaSO as both reductant and sulfone-source. The NaSO together with the electron-shuttle catalyst is crucial to divert the mechanistic pathway toward the formation of alkyl sulfone anion instead of the previously reported alkylmetal intermediates. Mechanistic studies allow the identification of carbon-centered alkyl radical and sulfur-centered alkyl sulfone radical, which are in equilibrium via capture or extrusion of SO and could be converted to alkyl sulfone anion accelerated by iron electron-shuttle catalysis, leading to the observed high chemoselectivity.

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