Manganese-Mediated C–C Bond Formation: Alkoxycarbonylation of Organoboranes

Robbert Van Putten; Georgy A. Filonenko; Annika M. Krieger; Martin Lutz; Evgeny A. Pidko

doi:10.1021/acs.organomet.0c00781

Manganese-Mediated C–C Bond Formation: Alkoxycarbonylation of Organoboranes

Robbert Van Putten, Georgy A. Filonenko, Annika M. Krieger, Martin Lutz, Evgeny A. Pidko

Inorganic Systems Engineering, Department of Chemical Engineering, Faculty of Applied Sciences, Delft University of Technology, Van der Maasweg 9, 2629 HZ Delft, The Netherlands

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C-C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester's substitution (e.g., OMe, OtBu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation.

Original language	English
Pages (from-to)	674-681
Number of pages	8
Journal	Organometallics
Volume	40
Issue number	6
DOIs	https://doi.org/10.1021/acs.organomet.0c00781
Publication status	Published - 22 Mar 2021

Bibliographical note

Funding Information:
Our investigation into the reactivity of Mn(CO)Br was preceded by DFT calculations from our group. These calculations suggested that nucleophiles (e.g., hydrides and alkoxides) could react with a Mn(I)-bound carbonyl ligand, thereby resulting in the formation of Mn formyl or acyl complexes (a). This finding was supported by results from a literature study. Experiments were performed to substantiate the computational results. 5

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© 2021 The Authors. Published by American Chemical Society.

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title = "Manganese-Mediated C–C Bond Formation: Alkoxycarbonylation of Organoboranes",

abstract = "Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C-C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester's substitution (e.g., OMe, OtBu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation. ",

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note = "Funding Information: Our investigation into the reactivity of Mn(CO)Br was preceded by DFT calculations from our group. These calculations suggested that nucleophiles (e.g., hydrides and alkoxides) could react with a Mn(I)-bound carbonyl ligand, thereby resulting in the formation of Mn formyl or acyl complexes (a). This finding was supported by results from a literature study. Experiments were performed to substantiate the computational results. 5 Publisher Copyright: {\textcopyright} {\textcopyright} 2021 The Authors. Published by American Chemical Society.",

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doi = "10.1021/acs.organomet.0c00781",

language = "English",

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AU - Van Putten, Robbert

AU - Filonenko, Georgy A.

AU - Krieger, Annika M.

AU - Lutz, Martin

AU - Pidko, Evgeny A.

N1 - Funding Information: Our investigation into the reactivity of Mn(CO)Br was preceded by DFT calculations from our group. These calculations suggested that nucleophiles (e.g., hydrides and alkoxides) could react with a Mn(I)-bound carbonyl ligand, thereby resulting in the formation of Mn formyl or acyl complexes (a). This finding was supported by results from a literature study. Experiments were performed to substantiate the computational results. 5 Publisher Copyright: © © 2021 The Authors. Published by American Chemical Society.

PY - 2021/3/22

Y1 - 2021/3/22

N2 - Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C-C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester's substitution (e.g., OMe, OtBu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation.

AB - Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C-C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester's substitution (e.g., OMe, OtBu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation.

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Manganese-Mediated C–C Bond Formation: Alkoxycarbonylation of Organoboranes

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