Rhodium-Catalyzed Oxidative Alkenylation of Anisole: Control of Regioselectivity

Reid, Christopher W.; Gunnoe, T. Brent

doi:10.1021/acs.organomet.4c00155

Rhodium-Catalyzed Oxidative Alkenylation of Anisole: Control of Regioselectivity

Journal Article · Thu Jun 13 00:00:00 EDT 2024 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.4c00155· OSTI ID:2377717

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University of Virginia, Charlottesville, VA (United States); University of Virginia
University of Virginia, Charlottesville, VA (United States)

We report the conversion of anisole and olefins to alkenyl anisoles via a transition metal-catalyzed arene C–H activation and olefin insertion mechanism. The catalyst precursor, [(η²-C₂H₄)₂Rh(μ-OAc)]₂, and the in situ oxidant Cu(OPiv)₂ (OPiv = pivalate) convert anisole and olefins (ethylene or propylene) to alkenyl anisoles. When ethylene is used as the olefin, the o/m/p ratio varies between approximately 1:3:1 (selective for 3-methoxystyrene) to 1:5:10 (selective for 4-methoxystyrene). When propylene is the olefin, the o/m/p regioselectivity varies between approximately 1:8:20 to 1:8.5:1. The o/m/p ratios depend on concentration of pivalic acid and olefin. For example, when using ethylene, at relatively high pivalic acid concentrations and low ethylene concentrations, the o/m/p regioselectivity is 1:3:1. Conversely, again for use of ethylene, at relatively low pivalic acid concentrations and high ethylene concentrations, the o/m/p regioselectivity is 1:5:10. Mechanistic studies of the conversion of anisole and olefins to alkenyl anisoles provides evidence that the regioselectivity is likely under Curtin-Hammett conditions.

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Research Organization:: University of Virginia, Charlottesville, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0000776

OSTI ID:: 2377717

Alternate ID(s):: OSTI ID: 2386942

Journal Information:: Organometallics, Journal Name: Organometallics Journal Issue: 12 Vol. 43; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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