Dual Nickel- and Photoredox-Catalyzed Enantioselective Desymmetrization of Cyclic meso-Anhydrides

Erin E. Stache; Tomislav Rovis; Abigail G. Doyle

doi:10.1002/anie.201700097

Dual Nickel- and Photoredox-Catalyzed Enantioselective Desymmetrization of Cyclic meso-Anhydrides

Erin E. Stache, Tomislav Rovis, Abigail G. Doyle

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107 Scopus citations

Abstract

The enantioselective desymmetrization of cyclic meso-anhydrides with benzyl trifluoroborates under nickel-photoredox catalysis is described. The reaction tolerates a variety of sterically and electronically different trifluoroborates, as well as structurally unique cyclic anhydrides. The trans isomer of the keto-acid products is also observed at varying levels dependent on the trifluoroborate identity and relative catalyst loading. A mechanism involving decarbonylation and Ni−C bond homolysis of a Ni^II adduct is proposed. This feature allows access to a trans keto-acid as the major product in high enantioselectivity from a cis meso anhydride.

Original language	English (US)
Pages (from-to)	3679-3683
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	13
DOIs	https://doi.org/10.1002/anie.201700097
State	Published - Mar 20 2017

All Science Journal Classification (ASJC) codes

General Chemistry
Catalysis

Keywords

asymmetric synthesis
cross-coupling
desymmetrization
nickel
photoredox catalysis

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10.1002/anie.201700097

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title = "Dual Nickel- and Photoredox-Catalyzed Enantioselective Desymmetrization of Cyclic meso-Anhydrides",

abstract = "The enantioselective desymmetrization of cyclic meso-anhydrides with benzyl trifluoroborates under nickel-photoredox catalysis is described. The reaction tolerates a variety of sterically and electronically different trifluoroborates, as well as structurally unique cyclic anhydrides. The trans isomer of the keto-acid products is also observed at varying levels dependent on the trifluoroborate identity and relative catalyst loading. A mechanism involving decarbonylation and Ni−C bond homolysis of a NiII adduct is proposed. This feature allows access to a trans keto-acid as the major product in high enantioselectivity from a cis meso anhydride.",

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T1 - Dual Nickel- and Photoredox-Catalyzed Enantioselective Desymmetrization of Cyclic meso-Anhydrides

AU - Stache, Erin E.

AU - Rovis, Tomislav

AU - Doyle, Abigail G.

PY - 2017/3/20

Y1 - 2017/3/20

N2 - The enantioselective desymmetrization of cyclic meso-anhydrides with benzyl trifluoroborates under nickel-photoredox catalysis is described. The reaction tolerates a variety of sterically and electronically different trifluoroborates, as well as structurally unique cyclic anhydrides. The trans isomer of the keto-acid products is also observed at varying levels dependent on the trifluoroborate identity and relative catalyst loading. A mechanism involving decarbonylation and Ni−C bond homolysis of a NiII adduct is proposed. This feature allows access to a trans keto-acid as the major product in high enantioselectivity from a cis meso anhydride.

AB - The enantioselective desymmetrization of cyclic meso-anhydrides with benzyl trifluoroborates under nickel-photoredox catalysis is described. The reaction tolerates a variety of sterically and electronically different trifluoroborates, as well as structurally unique cyclic anhydrides. The trans isomer of the keto-acid products is also observed at varying levels dependent on the trifluoroborate identity and relative catalyst loading. A mechanism involving decarbonylation and Ni−C bond homolysis of a NiII adduct is proposed. This feature allows access to a trans keto-acid as the major product in high enantioselectivity from a cis meso anhydride.

KW - asymmetric synthesis

KW - cross-coupling

KW - desymmetrization

KW - nickel

KW - photoredox catalysis

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JO - Angewandte Chemie - International Edition

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Dual Nickel- and Photoredox-Catalyzed Enantioselective Desymmetrization of Cyclic meso-Anhydrides

Abstract

All Science Journal Classification (ASJC) codes

Keywords

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