Synthesis of Sulfilimines Enabled by Copper-Catalyzed S-Arylation of Sulfenamides

Liang, Qingjin1,2,3; Wells, Lucille A.4; Han, Kaiming2,3,5; Chen, Shufeng5; Kozlowski, Marisa C.4; Jia, Tiezheng2,3,6

2023-03-01

10.1021/jacs.2c12947

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Impact Factor & Quartile

0002-7863

1520-5126

Herein, an unprecedented synthetic route to sulfilimines via a copper catalyzed Chan-Lam-type coupling of sulfenamides is presented. A key to success in this novel transformation is the chemoselective S-arylation of S(II) sulfenamides to form S(IV) sulfilimines, overriding the competitive, and more thermodynamically favored, C-N bond formation that does not require a change in the sulfur oxidation state. Computations reveal that the selectivity arises from a selective transmetallation event where bidentate sulfenamide coordination through the sulfur and oxygen atoms favors the S-arylation pathway. The mild and environmentally benign catalytic conditions enable broad functional group compatibility, allowing a variety of diaryl or alkyl aryl sulfilimines to be efficiently prepared. The Chan-Lam coupling procedure could also tolerate alkenylboronic acids as coupling partners to afford alkenyl aryl sulfilimines, a class of scaffolds that cannot be directly synthesized via conventional imination strategies. The benzoyl-protecting groups could be conveniently removed from the product, which, in turn, could be readily transformed into several S(IV) and S(VI) derivatives.

SCI

English

Corresponding

Guangdong-Joint Foundation of Shenzhen["2021B1515120046","2022B1515120075"] ; Natural Science Foundation of Guangdong Province[2022A1515011770] ; Science and Technology Innovation Commission of Shenzhen Municipality["JCYJ20220818101404010","20220815113214003"] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; NIH[R35 GM131902] ; null[22061031]

Chemistry

Chemistry, Multidisciplinary

WOS:000953113300001

AMER CHEMICAL SOC

Web of Science

1.Harbin Inst Technol, Sch Chem & Chem Engn, Harbin 150001, Peoples R China
2.Southern Univ Sci & Technol, Res Ctr Chem Biol & Om Anal, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
3.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China
4.Univ Penn, Dept Chem, Roy & Diana Vagelos Labs, Philadelphia, PA 19104 USA
5.Inner Mongolia Univ, Sch Chem & Chem Engn, P, R China, Hohhot 010021, Peoples R China
6.Nankai Univ, State Key Lab Elemento Organ Chem, Tianjin 300071, Peoples R China

Liang, Qingjin,Wells, Lucille A.,Han, Kaiming,et al. Synthesis of Sulfilimines Enabled by Copper-Catalyzed S-Arylation of Sulfenamides[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023.

Liang, Qingjin,Wells, Lucille A.,Han, Kaiming,Chen, Shufeng,Kozlowski, Marisa C.,&Jia, Tiezheng.(2023).Synthesis of Sulfilimines Enabled by Copper-Catalyzed S-Arylation of Sulfenamides.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.

Liang, Qingjin,et al."Synthesis of Sulfilimines Enabled by Copper-Catalyzed S-Arylation of Sulfenamides".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023).