Catalytic Desaturation of Aliphatic Amides and Imides Enabled by Excited-State Base-Metal Catalysis

Chenyang Wang; Luis Azofra Mesa; Phong Dam; Michael Sebek; Norbert Steinfeldt; Jabor Rabeah; Osama El-Sepelgy

doi:10.1021/acscatal.2c01723

Catalytic Desaturation of Aliphatic Amides and Imides Enabled by Excited-State Base-Metal Catalysis

Chenyang Wang, Luis Azofra Mesa, Phong Dam, Michael Sebek, Norbert Steinfeldt, Jabor Rabeah, Osama El-Sepelgy

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

21 Scopus citations

Abstract

Herein, we report a photoexcited base-metal-catalyzed selective desaturation of aliphatic amides and imides. The reaction is catalyzed by a base-metal cobalt complex under visible-light irradiation. This transformation can be efficiently processed at room temperature and enables the synthesis of valuable cyclic and acyclic enamides and enimides from abundant chemicals. Density functional theory (DFT) analysis, electron paramagnetic resonance (EPR), and UV–vis studies rationalized the discovered reactivity of the cobalt catalyst for the photochemical C(sp3)–H activation reaction. Finally, we demonstrated the potential of our process by scaling-up experiments using a continuous flow photoreactor.

Original language	English (US)
Pages (from-to)	8868-8876
Number of pages	9
Journal	ACS Catalysis
DOIs	https://doi.org/10.1021/acscatal.2c01723
State	Published - Jul 10 2022
Externally published	Yes

ASJC Scopus subject areas

Catalysis

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10.1021/acscatal.2c01723

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@article{d1cb25a6a15c4664b3ed30b34f44ff7c,

title = "Catalytic Desaturation of Aliphatic Amides and Imides Enabled by Excited-State Base-Metal Catalysis",

abstract = "Herein, we report a photoexcited base-metal-catalyzed selective desaturation of aliphatic amides and imides. The reaction is catalyzed by a base-metal cobalt complex under visible-light irradiation. This transformation can be efficiently processed at room temperature and enables the synthesis of valuable cyclic and acyclic enamides and enimides from abundant chemicals. Density functional theory (DFT) analysis, electron paramagnetic resonance (EPR), and UV–vis studies rationalized the discovered reactivity of the cobalt catalyst for the photochemical C(sp3)–H activation reaction. Finally, we demonstrated the potential of our process by scaling-up experiments using a continuous flow photoreactor.",

author = "Chenyang Wang and {Azofra Mesa}, Luis and Phong Dam and Michael Sebek and Norbert Steinfeldt and Jabor Rabeah and Osama El-Sepelgy",

note = "KAUST Repository Item: Exported on 2022-09-14 Acknowledgements: Prof. Dr. Matthias Beller is gratefully acknowledged for his continued generous support, and the paper is dedicated to him on the occasion of his 60th birthday. Gratitude is also due to KAUST for the use of supercomputer Shaheen II for providing the computational resources. This work was financially supported by Deutsche Forschungsgemeinschaft (DFG, Grant Number 456582392) and by the Leibniz Institute for Catalysis e.V. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2022",

month = jul,

day = "10",

doi = "10.1021/acscatal.2c01723",

language = "English (US)",

pages = "8868--8876",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

}

TY - JOUR

T1 - Catalytic Desaturation of Aliphatic Amides and Imides Enabled by Excited-State Base-Metal Catalysis

AU - Wang, Chenyang

AU - Azofra Mesa, Luis

AU - Dam, Phong

AU - Sebek, Michael

AU - Steinfeldt, Norbert

AU - Rabeah, Jabor

AU - El-Sepelgy, Osama

N1 - KAUST Repository Item: Exported on 2022-09-14 Acknowledgements: Prof. Dr. Matthias Beller is gratefully acknowledged for his continued generous support, and the paper is dedicated to him on the occasion of his 60th birthday. Gratitude is also due to KAUST for the use of supercomputer Shaheen II for providing the computational resources. This work was financially supported by Deutsche Forschungsgemeinschaft (DFG, Grant Number 456582392) and by the Leibniz Institute for Catalysis e.V. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2022/7/10

Y1 - 2022/7/10

N2 - Herein, we report a photoexcited base-metal-catalyzed selective desaturation of aliphatic amides and imides. The reaction is catalyzed by a base-metal cobalt complex under visible-light irradiation. This transformation can be efficiently processed at room temperature and enables the synthesis of valuable cyclic and acyclic enamides and enimides from abundant chemicals. Density functional theory (DFT) analysis, electron paramagnetic resonance (EPR), and UV–vis studies rationalized the discovered reactivity of the cobalt catalyst for the photochemical C(sp3)–H activation reaction. Finally, we demonstrated the potential of our process by scaling-up experiments using a continuous flow photoreactor.

AB - Herein, we report a photoexcited base-metal-catalyzed selective desaturation of aliphatic amides and imides. The reaction is catalyzed by a base-metal cobalt complex under visible-light irradiation. This transformation can be efficiently processed at room temperature and enables the synthesis of valuable cyclic and acyclic enamides and enimides from abundant chemicals. Density functional theory (DFT) analysis, electron paramagnetic resonance (EPR), and UV–vis studies rationalized the discovered reactivity of the cobalt catalyst for the photochemical C(sp3)–H activation reaction. Finally, we demonstrated the potential of our process by scaling-up experiments using a continuous flow photoreactor.

UR - http://hdl.handle.net/10754/679645

UR - https://pubs.acs.org/doi/10.1021/acscatal.2c01723

U2 - 10.1021/acscatal.2c01723

DO - 10.1021/acscatal.2c01723

M3 - Article

SN - 2155-5435

SP - 8868

EP - 8876

JO - ACS Catalysis

JF - ACS Catalysis

ER -

Catalytic Desaturation of Aliphatic Amides and Imides Enabled by Excited-State Base-Metal Catalysis

Abstract

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