Angewandte Chemie · 2019 · 13 citations · 61 references
Natural SciencesChemical EngineeringChemistryCatalysisOrganic ChemistryOrganometallic ChemistryCross-coupling ReactionsHeterocyclic ChemistryOrganic SynthesisReaction MechanismsCatalytic Cycle MechanismsChain-walking MechanismsConjugated DienesHeterocycle FunctionalizationOrganic Molecule SynthesisPalladium CatalystsRing-forming ReactionsTransition-metal-catalyzed Functionalization
Abstract Sequential formation of distant bonds in organic molecules was achieved for the palladium‐catalyzed hydrosilylation/cyclization of various 1, n ‐dienes by chain walking of the metal catalyst. The reaction was applicable to various 1, n ‐dienes, including a 1,13‐diene, to form a cyclopentane ring as well as a carbon–silicon bond at a remote site. The use of “nondissociative” chain walking provides a fascinating strategy in organic synthesis to functionalize distant parts of organic molecules, in a particular order, within a catalytic cycle by effectively moving the reactive center from a remote position.
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Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide
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