键裂
化学
芳基
直接的
环加成
吲哚试验
立体化学
芳构化
芳基
劈理(地质)
吲哚
MINDO公司
分子
光化学
组合化学
催化作用
物理
有机化学
材料科学
核物理学
激发态
复合材料
烷基
断裂(地质)
单重态
作者
Guangjin Zhen,Guohui Zeng,Kai Jiang,Furong Wang,Xiaohui Cao,Biaolin Yin
标识
DOI:10.1002/chem.202203217
摘要
When mono-radical ipso-cyclization of aryl sulfonamides tend to undergo Smiles-type rearrangement through aromatization-driven C-S bond cleavage, diradical-mediated cyclization must perform in a distinct reaction pathway. It is interesting meanwhile challenging to tune the rate of C-S bond cleavage to achieve a chemically divergent reaction of (hetero) aryl sulfonamides in a visible-light induced energy transfer (EnT) reaction pathway involving diradical species. Herein a chemically divergent reaction based on the designed indole-tethered (hetero)arylsulfonamides is reported which involves a diradical-mediated ipso-cyclization and a controllable cleavage of an inherent C-S bond. The combined experimental and computational results have revealed that the cleavage of the C-S bond in these substrates can be controlled by tuning the heteroaryl moieties: a) If the (hetero)aryl is thienyl, furyl, phenanthryl, etc., the radical coupling of double dearomative diradicals (DDDR) precedes over C-S bond cleavage to afford cyclobutene fused indolines by double dearomative [2+2]-cycloaddition; b) if the (hetero)aryl is phenyl, naphthyl, pyridyl, indolyl etc., the cleavage of C-S bond in DDDR is favored over radical coupling to afford biaryl products.
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