Catalytic arylsulfonyl radical-triggered 1,5-enyne-bicyclizations and hydrosulfonylation of α,β-conjugates

被引：154

作者：

Chen, Zhen-Zhen ^{[1
]}

Liu, Shuai ^{[1
]}

Hao, Wen-Juan ^{[1
]}

Xu, Ge ^{[1
]}

Wu, Shuo ^{[1
]}

Miao, Jiao-Na ^{[1
]}

Jiang, Bo ^{[1
]}

Wang, Shu-Liang ^{[1
]}

Tu, Shu-Jiang ^{[1
]}

Li, Guigen ^{[2
,3
]}

机构：

[1] Jiangsu Normal Univ, Jiangsu Key Lab Green Synthet Chem Funct Mat, Xuzhou 211116, Peoples R China

[2] Nanjing Univ, Sch Chem & Chem Eng, Collaborat Innovat Ctr Chem Life Sci, Inst Chem & BioMed Sci, Nanjing 210093, Jiangsu, Peoples R China

[3] Texas Tech Univ, Dept Chem & Biochem, Lubbock, TX 79409 USA

来源：

CHEMICAL SCIENCE | 2015年 / 6卷 / 11期

关键词：

CYCLIZATION-ELIMINATION REACTION; ACTIVATED ALKENES; ELECTROPHILIC CYCLIZATION; STEREOSELECTIVE-SYNTHESIS; BOND FUNCTIONALIZATION; OXIDATIVE CYCLIZATION; SULFONYL HYDRAZIDES; ENYNE CYCLIZATIONS; TANDEM CYCLIZATION; CASCADE REACTIONS;

D O I：

10.1039/c5sc02343b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A catalytic bicyclization reaction of 1,5-enynes anchored by alpha, beta-conjugates with arylsulfonyl radicals generated in situ from sulfonyl hydrazides has been established using TBAI (20 mol%) and Cu(OAc)(2) (5 mol%) as co-catalysts under convenient conditions. In addition, the use of benzoyl peroxide (BPO) as the oxidant and pivalic acid (PivOH) as an additive was proven to be necessary for this reaction. The reactions occurred through 5-exo-dig/6-endo-trig bicyclizations and homolytic aromatic substitution (HAS) cascade mechanisms to give benzo[b] fluorens regioselectively. A similar catalytic process was developed for the synthesis of gamma-ketosulfones. These reactions feature readily accessible starting materials and simple one-pot operation.

引用

页码：6654 / 6658

页数：5

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