Stereodivergent, Kinetically Controlled Isomerization of Terminal Alkenes via Nickel Catalysis

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Abstract: Because internal alkenes are more challenging synthetic targets than terminal alkenes, metal‐catalyzed olefin mono‐transposition (i.e., positional isomerization) approaches have emerged to afford valuable E‐ or Z‐ internal alkenes from their complementary terminal alkene feedstocks. However, the applicability of these methods has been hampered by lack of generality, commercial availability of precatalysts, and scalability. Here, we report a nickel‐catalyzed platform for the stereodivergent E/Z‐selective synthesis of internal alkenes at room temperature. Commercial reagents enable this one‐carbon transposition of terminal alkenes to valuable E‐ or Z‐internal alkenes via a Ni−H‐mediated insertion/elimination mechanism. Though the mechanistic regime is the same in both systems, the underlying pathways that lead to each of the active catalysts are distinct, with the Z‐selective catalyst forming from comproportionation of an oxidative addition complex followed by oxidative addition with substrate and the E‐selective catalyst forming from protonation of the metal by the trialkylphosphonium salt additive. In each case, ligand sterics and denticity control stereochemistry and prevent over‐isomerization.

Location: Deutsche Nationalbibliothek Frankfurt am Main

Extent: Online-Ressource

Language: Englisch

Bibliographic citation: Stereodivergent, Kinetically Controlled Isomerization of Terminal Alkenes via Nickel Catalysis ; day:18 ; month:04 ; year:2024 ; extent:11
Angewandte Chemie / International edition. International edition ; (18.04.2024) (gesamt 11)

Creator: Rubel, Camille Z.
Ravn, Anne K.
Ho, Hang Chi
Yang, Shenghua
Li, Zi‐Qi
Engle, Keary
Vantourout, Julien C.

DOI: 10.1002/anie.202320081

URN: urn:nbn:de:101:1-2404181429408.188927216865

Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.

Last update: 14.08.2025, 10:46 AM CEST

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Associated

Rubel, Camille Z.
Ravn, Anne K.
Ho, Hang Chi
Yang, Shenghua
Li, Zi‐Qi
Engle, Keary
Vantourout, Julien C.

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