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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 valuableE‐ orZ‐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 stereodivergentE/Z‐selective synthesis of internal alkenes at room temperature. Commercial reagents enable this one‐carbon transposition of terminal alkenes to valuableE‐ orZ‐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 theZ‐selective catalyst forming from comproportionation of an oxidative addition complex followed by oxidative addition with substrate and theE‐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.
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Catalytic Hydrogenation of Terminal Alkenes by a (PPP) Pincer-Ligated Cobalt(II) Complex
A Co(II) complex, (PPHP)CoI2, was synthesized and evaluated as a precatalyst for the hydrogenation of terminal alkenes under mild conditions (1 atm H2, ambient temperature) using KBEt3H as an activator. This catalytic system was found to be active for terminal alkene substrates, including 1,1′-disubstituted alkenes, and to exhibit modest air and moisture stability. A preliminary investigation into substrate scope and functional group tolerance was performed. Upon the completion of catalytic reactions, the sole metal complex observed was identified as the dimeric species [(PPP)CoH]2 suggesting that the catalytically active species may be a cobalt hydride monomer.
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- Award ID(s):
- 2101002
- PAR ID:
- 10422231
- Date Published:
- Journal Name:
- Organometallics
- ISSN:
- 0276-7333
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.organomet.3c00170
