Synthesis of α-Aryl Primary Amides from α-Silyl Nitriles and Aryl Sulfoxides through [3,3]-Sigmatropic Rearrangement

Fan Luo; Hui Zhou; Xiao Bei Chen; Xue Jun Liu; Xiao Dong Chen; Peng Fei Qian; Xin Ping Wu; Wei Wang; Shi Lei Zhang

doi:10.1021/acs.orglett.2c00334

Synthesis of α-Aryl Primary Amides from α-Silyl Nitriles and Aryl Sulfoxides through [3,3]-Sigmatropic Rearrangement

Fan Luo, Hui Zhou, Xiao Bei Chen, Xue Jun Liu, Xiao Dong Chen, Peng Fei Qian, Xin Ping Wu, Wei Wang, Shi Lei Zhang

Pharmacology and Toxicology

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Abstract

A simple and efficient protocol was developed for the preparation of challenging α-aryl primary amides. This metal-free coupling process was triggered by TfOH-promoted electrophilic activation of α-silyl nitrile to generate keteniminium ion species, followed by reaction with aryl sulfoxide through [3,3]-sigmatrophic rearrangement to provide the target product. To the best of our knowledge, α-silyl nitrile has been rarely used as a pro-electrophilic reagent. Computational investigations confirmed the transient existence of a highly electrophilic keteniminium intermediate.

Original language	English (US)
Pages (from-to)	1700-1705
Number of pages	6
Journal	Organic Letters
Volume	24
Issue number	8
DOIs	https://doi.org/10.1021/acs.orglett.2c00334
State	Published - Mar 4 2022

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/acs.orglett.2c00334

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title = "Synthesis of α-Aryl Primary Amides from α-Silyl Nitriles and Aryl Sulfoxides through [3,3]-Sigmatropic Rearrangement",

abstract = "A simple and efficient protocol was developed for the preparation of challenging α-aryl primary amides. This metal-free coupling process was triggered by TfOH-promoted electrophilic activation of α-silyl nitrile to generate keteniminium ion species, followed by reaction with aryl sulfoxide through [3,3]-sigmatrophic rearrangement to provide the target product. To the best of our knowledge, α-silyl nitrile has been rarely used as a pro-electrophilic reagent. Computational investigations confirmed the transient existence of a highly electrophilic keteniminium intermediate.",

author = "Fan Luo and Hui Zhou and Chen, {Xiao Bei} and Liu, {Xue Jun} and Chen, {Xiao Dong} and Qian, {Peng Fei} and Wu, {Xin Ping} and Wei Wang and Zhang, {Shi Lei}",

note = "Funding Information: This work was supported by the National Natural Science Foundation of China (22071053 and 21202112), Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism (Shanghai Municipal Education Commission, grant 2021 Sci & Tech 03-28), the East China University of Science and Technology, the “111” Project, and PAPD (A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions). Publisher Copyright: {\textcopyright} 2022 American Chemical Society",

year = "2022",

month = mar,

day = "4",

doi = "10.1021/acs.orglett.2c00334",

language = "English (US)",

volume = "24",

pages = "1700--1705",

journal = "Organic Letters",

issn = "1523-7060",

publisher = "American Chemical Society",

number = "8",

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T1 - Synthesis of α-Aryl Primary Amides from α-Silyl Nitriles and Aryl Sulfoxides through [3,3]-Sigmatropic Rearrangement

AU - Luo, Fan

AU - Zhou, Hui

AU - Chen, Xiao Bei

AU - Liu, Xue Jun

AU - Chen, Xiao Dong

AU - Qian, Peng Fei

AU - Wu, Xin Ping

AU - Wang, Wei

AU - Zhang, Shi Lei

N1 - Funding Information: This work was supported by the National Natural Science Foundation of China (22071053 and 21202112), Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism (Shanghai Municipal Education Commission, grant 2021 Sci & Tech 03-28), the East China University of Science and Technology, the “111” Project, and PAPD (A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions). Publisher Copyright: © 2022 American Chemical Society

PY - 2022/3/4

Y1 - 2022/3/4

N2 - A simple and efficient protocol was developed for the preparation of challenging α-aryl primary amides. This metal-free coupling process was triggered by TfOH-promoted electrophilic activation of α-silyl nitrile to generate keteniminium ion species, followed by reaction with aryl sulfoxide through [3,3]-sigmatrophic rearrangement to provide the target product. To the best of our knowledge, α-silyl nitrile has been rarely used as a pro-electrophilic reagent. Computational investigations confirmed the transient existence of a highly electrophilic keteniminium intermediate.

AB - A simple and efficient protocol was developed for the preparation of challenging α-aryl primary amides. This metal-free coupling process was triggered by TfOH-promoted electrophilic activation of α-silyl nitrile to generate keteniminium ion species, followed by reaction with aryl sulfoxide through [3,3]-sigmatrophic rearrangement to provide the target product. To the best of our knowledge, α-silyl nitrile has been rarely used as a pro-electrophilic reagent. Computational investigations confirmed the transient existence of a highly electrophilic keteniminium intermediate.

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JO - Organic Letters

JF - Organic Letters

IS - 8

ER -

Synthesis of α-Aryl Primary Amides from α-Silyl Nitriles and Aryl Sulfoxides through [3,3]-Sigmatropic Rearrangement

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CCDC 2101825: Experimental Crystal Structure Determination

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Synthesis of α-Aryl Primary Amides from α-Silyl Nitriles and Aryl Sulfoxides through [3,3]-Sigmatropic Rearrangement

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CCDC 2101825: Experimental Crystal Structure Determination

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