Suzuki–Miyaura Cross-Coupling of Amides by N–C Cleavage Mediated by Air-Stable, Well-Defined [Pd(NHC)(sulfide)Cl2] Catalysts: Reaction Development, Scope, and Mechanism

Shiyi Yang; Xiang Yu; Yaxu Liu; Michele Tomasini; Lucia Caporaso; Albert Poater; Luigi Cavallo; Catherine S. J. Cazin; Steven P. Nolan; Michal Szostak

doi:10.1021/acs.joc.3c00912

Suzuki–Miyaura Cross-Coupling of Amides by N–C Cleavage Mediated by Air-Stable, Well-Defined [Pd(NHC)(sulfide)Cl2] Catalysts: Reaction Development, Scope, and Mechanism

Shiyi Yang, Xiang Yu, Yaxu Liu, Michele Tomasini, Lucia Caporaso, Albert Poater, Luigi Cavallo, Catherine S. J. Cazin, Steven P. Nolan, Michal Szostak

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

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Abstract

The Suzuki–Miyaura cross-coupling of amides by selective N–C acyl bond cleavage represents a powerful tool for constructing biaryl ketones from historically inert amide bonds. These amide bond activation reactions hinge upon efficient oxidative addition of the N–C acyl bond to Pd(0). However, in contrast to the well-researched activation of aryl halides by C(sp2)–X oxidative addition, very few studies on the mechanism of C(acyl)–N bond oxidative addition and catalyst effect have been reported. Herein, we report a study on [Pd(NHC)(sulfide)Cl2] catalysts in amide N–C bond activation. These readily prepared, well-defined, air- and moisture-stable Pd(II)–NHC catalysts feature SMe2 (DMS = dimethylsulfide) or S(CH2CH2)2 (THT = tetrahydrothiophene) as ancillary ligands. The reaction development, kinetic studies, and reaction scope are presented. Extensive DFT studies were conducted to gain insight into the mechanism of C(acyl)–N bond oxidative addition and catalyst activation. We expect that [Pd(NHC)(sulfide)Cl2] precatalysts featuring sulfides as well-defined, readily accessible ancillary ligands will find application in C(acyl)–X bond activation in organic synthesis and catalysis.

Original language	English (US)
Journal	The Journal of Organic Chemistry
DOIs	https://doi.org/10.1021/acs.joc.3c00912
State	Published - Jul 19 2023

Bibliographical note

KAUST Repository Item: Exported on 2023-07-24
Acknowledgements: We thank Rutgers University, the NSF (CAREER CHE-1650766), and the NIH (R35GM133326) for generous financial support. Supplement funding for this project was provided by the Rutgers University – Newark Chancellor’s Research Office. The 500 MHz spectrometer used in this study was supported by the NSF-MRI grant (CHE-1229030). A.P. is a Serra Húnter Fellow and ICREA Academia Prize 2019, and thanks the Spanish Ministerio de Ciencia e Innovación for a project PID2021-127423NB-I00 and the Generalitat de Catalunya for project 2021SGR623. S.P.N. thanks the BOF research fund, as well as the SBO projects CO2perate and D2M, for financial support. C.S.J.C. (G0C5423N) and S.P.N. (G0A6823N) thank the FWO for support. Y.L. thanks the CSC for a Ph.D. fellowship.

ASJC Scopus subject areas

Organic Chemistry

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10.1021/acs.joc.3c00912

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Yang, S., Yu, X., Liu, Y., Tomasini, M., Caporaso, L., Poater, A., Cavallo, L., Cazin, C. S. J., Nolan, S. P., & Szostak, M. (2023). Suzuki–Miyaura Cross-Coupling of Amides by N–C Cleavage Mediated by Air-Stable, Well-Defined [Pd(NHC)(sulfide)Cl2] Catalysts: Reaction Development, Scope, and Mechanism. The Journal of Organic Chemistry. https://doi.org/10.1021/acs.joc.3c00912

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title = "Suzuki–Miyaura Cross-Coupling of Amides by N–C Cleavage Mediated by Air-Stable, Well-Defined [Pd(NHC)(sulfide)Cl2] Catalysts: Reaction Development, Scope, and Mechanism",

abstract = "The Suzuki–Miyaura cross-coupling of amides by selective N–C acyl bond cleavage represents a powerful tool for constructing biaryl ketones from historically inert amide bonds. These amide bond activation reactions hinge upon efficient oxidative addition of the N–C acyl bond to Pd(0). However, in contrast to the well-researched activation of aryl halides by C(sp2)–X oxidative addition, very few studies on the mechanism of C(acyl)–N bond oxidative addition and catalyst effect have been reported. Herein, we report a study on [Pd(NHC)(sulfide)Cl2] catalysts in amide N–C bond activation. These readily prepared, well-defined, air- and moisture-stable Pd(II)–NHC catalysts feature SMe2 (DMS = dimethylsulfide) or S(CH2CH2)2 (THT = tetrahydrothiophene) as ancillary ligands. The reaction development, kinetic studies, and reaction scope are presented. Extensive DFT studies were conducted to gain insight into the mechanism of C(acyl)–N bond oxidative addition and catalyst activation. We expect that [Pd(NHC)(sulfide)Cl2] precatalysts featuring sulfides as well-defined, readily accessible ancillary ligands will find application in C(acyl)–X bond activation in organic synthesis and catalysis.",

author = "Shiyi Yang and Xiang Yu and Yaxu Liu and Michele Tomasini and Lucia Caporaso and Albert Poater and Luigi Cavallo and Cazin, {Catherine S. J.} and Nolan, {Steven P.} and Michal Szostak",

note = "KAUST Repository Item: Exported on 2023-07-24 Acknowledgements: We thank Rutgers University, the NSF (CAREER CHE-1650766), and the NIH (R35GM133326) for generous financial support. Supplement funding for this project was provided by the Rutgers University – Newark Chancellor{\textquoteright}s Research Office. The 500 MHz spectrometer used in this study was supported by the NSF-MRI grant (CHE-1229030). A.P. is a Serra H{\'u}nter Fellow and ICREA Academia Prize 2019, and thanks the Spanish Ministerio de Ciencia e Innovaci{\'o}n for a project PID2021-127423NB-I00 and the Generalitat de Catalunya for project 2021SGR623. S.P.N. thanks the BOF research fund, as well as the SBO projects CO2perate and D2M, for financial support. C.S.J.C. (G0C5423N) and S.P.N. (G0A6823N) thank the FWO for support. Y.L. thanks the CSC for a Ph.D. fellowship.",

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doi = "10.1021/acs.joc.3c00912",

language = "English (US)",

journal = "The Journal of Organic Chemistry",

issn = "0022-3263",

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T1 - Suzuki–Miyaura Cross-Coupling of Amides by N–C Cleavage Mediated by Air-Stable, Well-Defined [Pd(NHC)(sulfide)Cl2] Catalysts: Reaction Development, Scope, and Mechanism

AU - Yang, Shiyi

AU - Yu, Xiang

AU - Liu, Yaxu

AU - Tomasini, Michele

AU - Caporaso, Lucia

AU - Poater, Albert

AU - Cavallo, Luigi

AU - Cazin, Catherine S. J.

AU - Nolan, Steven P.

AU - Szostak, Michal

N1 - KAUST Repository Item: Exported on 2023-07-24 Acknowledgements: We thank Rutgers University, the NSF (CAREER CHE-1650766), and the NIH (R35GM133326) for generous financial support. Supplement funding for this project was provided by the Rutgers University – Newark Chancellor’s Research Office. The 500 MHz spectrometer used in this study was supported by the NSF-MRI grant (CHE-1229030). A.P. is a Serra Húnter Fellow and ICREA Academia Prize 2019, and thanks the Spanish Ministerio de Ciencia e Innovación for a project PID2021-127423NB-I00 and the Generalitat de Catalunya for project 2021SGR623. S.P.N. thanks the BOF research fund, as well as the SBO projects CO2perate and D2M, for financial support. C.S.J.C. (G0C5423N) and S.P.N. (G0A6823N) thank the FWO for support. Y.L. thanks the CSC for a Ph.D. fellowship.

PY - 2023/7/19

Y1 - 2023/7/19

N2 - The Suzuki–Miyaura cross-coupling of amides by selective N–C acyl bond cleavage represents a powerful tool for constructing biaryl ketones from historically inert amide bonds. These amide bond activation reactions hinge upon efficient oxidative addition of the N–C acyl bond to Pd(0). However, in contrast to the well-researched activation of aryl halides by C(sp2)–X oxidative addition, very few studies on the mechanism of C(acyl)–N bond oxidative addition and catalyst effect have been reported. Herein, we report a study on [Pd(NHC)(sulfide)Cl2] catalysts in amide N–C bond activation. These readily prepared, well-defined, air- and moisture-stable Pd(II)–NHC catalysts feature SMe2 (DMS = dimethylsulfide) or S(CH2CH2)2 (THT = tetrahydrothiophene) as ancillary ligands. The reaction development, kinetic studies, and reaction scope are presented. Extensive DFT studies were conducted to gain insight into the mechanism of C(acyl)–N bond oxidative addition and catalyst activation. We expect that [Pd(NHC)(sulfide)Cl2] precatalysts featuring sulfides as well-defined, readily accessible ancillary ligands will find application in C(acyl)–X bond activation in organic synthesis and catalysis.

AB - The Suzuki–Miyaura cross-coupling of amides by selective N–C acyl bond cleavage represents a powerful tool for constructing biaryl ketones from historically inert amide bonds. These amide bond activation reactions hinge upon efficient oxidative addition of the N–C acyl bond to Pd(0). However, in contrast to the well-researched activation of aryl halides by C(sp2)–X oxidative addition, very few studies on the mechanism of C(acyl)–N bond oxidative addition and catalyst effect have been reported. Herein, we report a study on [Pd(NHC)(sulfide)Cl2] catalysts in amide N–C bond activation. These readily prepared, well-defined, air- and moisture-stable Pd(II)–NHC catalysts feature SMe2 (DMS = dimethylsulfide) or S(CH2CH2)2 (THT = tetrahydrothiophene) as ancillary ligands. The reaction development, kinetic studies, and reaction scope are presented. Extensive DFT studies were conducted to gain insight into the mechanism of C(acyl)–N bond oxidative addition and catalyst activation. We expect that [Pd(NHC)(sulfide)Cl2] precatalysts featuring sulfides as well-defined, readily accessible ancillary ligands will find application in C(acyl)–X bond activation in organic synthesis and catalysis.

UR - http://hdl.handle.net/10754/693175

UR - https://pubs.acs.org/doi/10.1021/acs.joc.3c00912

U2 - 10.1021/acs.joc.3c00912

DO - 10.1021/acs.joc.3c00912

M3 - Article

C2 - 37467445

SN - 0022-3263

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

ER -

Suzuki–Miyaura Cross-Coupling of Amides by N–C Cleavage Mediated by Air-Stable, Well-Defined [Pd(NHC)(sulfide)Cl2] Catalysts: Reaction Development, Scope, and Mechanism

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