Rhodium-Catalyzed Alkenylation of Arenes with Multi-Substituted Olefins: Comparison of Selectivity and Reaction Rate as a Function of Olefin Identity

Bennett, Marc T.; Reid, Christopher W.; Musgrave, Charles B.; Goddard, William A.; Gunnoe, T. Brent

doi:10.1021/acs.organomet.3c00073

Title: Rhodium-Catalyzed Alkenylation of Arenes with Multi-Substituted Olefins: Comparison of Selectivity and Reaction Rate as a Function of Olefin Identity

Journal Article · 08 May 2023 · Organometallics

DOI: https://doi.org/10.1021/acs.organomet.3c00073 · OSTI ID:1974538

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Univ. of Virginia, Charlottesville, VA (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States)

Rhodium-catalyzed arene alkenylation using Cu(II) carboxylates as the in situ oxidant and mono-substituted olefins has been previously reported (e.g., J. Am. Chem. Soc. 2019, 139, 5474; J. Am. Chem. Soc. 2018, 140, 17007; Organometallics 2019, 38, 3860; J. Am. Chem. Soc. 2020, 142, 10534). Herein, studies are extended to multi-substituted olefins with the goal of evaluating the effect of olefin substitution pattern and substituent identity on selectivity and turnover frequency. The influence of olefin substitution is probed by comparing the conversion of benzene to alkenyl arenes with ethylene, propylene, 1-butene, cis-2-butene, trans-2-butene, isobutene, 2-methyl-2-butene, and tetramethylethylene as well as the phenyl-substituted olefins and isomers of propenylbenzene. The rate of oxidative hydrophenylation for multi-substituted olefins follows the trend monosubstituted > disubstituted > trisubstituted, and tetrasubstituted olefins are unreactive. To probe the effect of substituent size on Markovnikov/ anti-Markovnikov regioselectivity, cyclohexyl, tert-butyl, isopropyl, ethyl, and methyl substituted α-olefins are compared. Selectivity for anti-Markovnikov products generally increases as substituent steric bulk is increased. Tolerance for some functionalized olefins is demonstrated. Here, the ortho/meta/para regioselectivity with mono-substituted arenes reveals that arene and olefin identity influences selectivity. Further mechanistic studies provide evidence for Curtin–Hammet control of ortho/meta/para regioselectivity with monosubstituted arenes.

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Research Organization:: Univ. 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:: 1974538

Journal Information:: Organometallics, Vol. 42, Issue 10; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Rhodium-Catalyzed Alkenylation of Arenes with Multi-Substituted Olefins: Comparison of Selectivity and Reaction Rate as a Function of Olefin Identity

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