Rhodium‐Catalyzed Oxidative Alkenylation of Naphthalene: Factors That Influence Reaction at the β‐ versus α‐Position

Reid, Christopher W.; Baptiste, Lauren E.; Gunnoe, T. Brent

doi:10.1002/cctc.202500150

Rhodium‐Catalyzed Oxidative Alkenylation of Naphthalene: Factors That Influence Reaction at the β‐ versus α‐Position

Journal Article · Thu Apr 10 00:00:00 EDT 2025 · ChemCatChem

DOI:https://doi.org/10.1002/cctc.202500150· OSTI ID:2554103

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Department of Chemistry University of Virginia Charlottesville VA 22904 USA

Abstract

The catalyst precursor [(η ² ‐C ₂ H ₄ ) ₂ Rh(μ‐OAc)] ₂ and in situ oxidant Cu(OPiv) ₂ (OPiv = t ‐BuCOO ^– ) convert naphthalene and olefins (i.e., ethylene and propylene) to alkenylnaphthalenes. Under all reaction conditions tested, the functionalization is selective for the β‐position of naphthalene with the highest observed β:α ratio >20:1. The β‐selectivity is catalyst controlled, but oxidant identity, ethylene pressure, and olefin identity influence the ratio of β‐alkenylation to α‐alkenylation. The concentration of HOPiv and naphthalene do not have an effect on the β:α ratio under the reaction conditions tested. Arenes similar to naphthalene (i.e., o‐ xylene and 1,2,3,4‐tetrahydronaphthalene) give quantitative selectivity for alkenylation at the position β to the substituent. Using propylene as the olefin for naphthalene alkenylation, the β:α ratio is 32(7):1. and the anti‐Markovnikov to Markovnikov ratio is 16(2):1.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0000776

OSTI ID:: 2554103

Alternate ID(s):: OSTI ID: 2554106

Journal Information:: ChemCatChem, Journal Name: ChemCatChem; ISSN 1867-3880

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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