Metal-Hydride C-C Cross-Coupling of Alkenes Through a Double Outer-Sphere Mechanism.

J Org Chem

Department of Chemistry, Scripps Research, La Jolla, California 92037, United States.

Published: November 2024

AI Article Synopsis

  • * Traditional methods typically use inner-sphere reactions, where alkenes are part of the metal's ligand environment during the reaction.
  • * This outer-sphere reaction strategy is particularly significant for synthesizing complex molecular targets, especially in challenging couplings relevant to natural products.*

Article Abstract

This Synopsis covers recent reports of metal-catalyzed alkene functionalizations that likely involve iterative outer-sphere reactions in which the substrate reacts directly with a metal ligand instead of with the metal center itself. Traditional metal hydride-catalyzed alkene functionalizations involve this latter pathway whereby the alkene forms part of the metal ligand sphere (i.e. an inner-sphere reaction). In contrast, alkenes do not ligate the metal in so-called outer-sphere reactions and instead react with a metal ligand. These transformations have proved crucial for the synthesis of high fraction sp (F3) targets, especially in hindered fragment couplings of relevance to natural product space.

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http://dx.doi.org/10.1021/acs.joc.4c00260DOI Listing

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