Catalytic Decarboxylative Radical Sulfonylation

被引：108

作者：

He, Jiayan ^{[1
,2
]}

Chen, Guangle ^{[3
,4
]}

Zhang, Benxiang ^{[1
,2
]}

Li, Yi ^{[1
,2
]}

Chen, Jia-Rong ^{[5
]}

Xiao, Wen-Jing ^{[5
]}

Liu, Feng ^{[3
,4
]}

Li, Chaozhong ^{[1
,2
]}

机构：

[1] Chinese Acad Sci, Key Lab Organofluorine Chem, Shanghai Inst Organ Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China

[2] Chinese Acad Sci, Collaborat Innovat Ctr Chem Life Sci, Shanghai Inst Organ Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China

[3] Soochow Univ, Jiangsu Key Lab Neuropsychiat Dis, Coll Pharmaceut Sci, 199 Ren Ai Rd, Suzhou 215123, Jiangsu, Peoples R China

[4] Soochow Univ, Dept Med Chem, Coll Pharmaceut Sci, 199 Ren Ai Rd, Suzhou 215123, Jiangsu, Peoples R China

[5] Cent China Normal Univ, CCNU uOttawa Joint Res Ctr, Hubei Int Sci & Technol Cooperat Base Pesticide &, Key Lab Pesticides & Chem Biol,Minist Educ,Coll C, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China

来源：

CHEM | 2020年 / 6卷 / 05期

基金：

中国国家自然科学基金;

关键词：

REDOX-ACTIVE ESTERS; PHOTOREDOX CATALYSIS; ALKYL RADICALS; SULFUR-DIOXIDE; RATE CONSTANTS; TRIFLUOROMETHYLATION;

D O I：

10.1016/j.chempr.2020.02.003

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Sulfones are key structural motifs in pharmaceuticals and agrochemicals, and their synthesis is of paramount importance in organic chemistry. While nucleophilic and electrophilic C(sp(3))-sulfonylation are well documented, radical C(sp(3))-sulfonylation remains elusive. Herein, we report the decarboxylative radical sulfonylation with sulfinates. With the merger of 4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene) and Cu(OTf)(2) as catalysts, the visible-light-induced reaction of redox-active esters of aliphatic carboxylic acids with organosulfinates at room temperature provides the corresponding decarboxylative sulfonylation products in satisfactory yields. This redox-neutral protocol exhibits broad substrate scope and wide functional group compatibility, enabling the late-stage modification of complex natural products and bioactive pharmaceuticals. The synthetic utility of the method is further demonstrated by the improved synthesis of anti-prostate cancer drug bicalutamide. A mechanism involving sulfonyl group transfer from Cu(II)-SO2R to alkyl radicals is proposed.

引用

页码：1149 / 1159

页数：11

共 52 条

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