Aryne 1,2,3,5-Tetrasubstitution Enabled by 3-Silylaryne and Allyl Sulfoxide via an Aromatic 1,3-Silyl Migration
Aryne 1,2,3,5-Tetrasubstitution Enabled by 3-Silylaryne and Allyl Sulfoxide via an Aromatic 1,3-Silyl Migration
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3-甲硅烷基芳基和烯丙基亚砜通过芳香族 1,3-甲硅烷基迁移实现芳炔 1,2,3,5-四取代
DOI：
10.1021/jacs.0c11119
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发表时间：
2021
影响因子：
15
通讯作者：
Yang Li
中科院分区：
文献类型：
--
作者：
Jiarong Shi;Lianggui Li;Chunhui Shan;Junli Wang;Zhonghong Chen;Rongrong Gu;Jia He;Min Tan;Yu Lan;Yang Li
尽管众所周知，苯炔可以作为合成子，可以方便地制备各种 1,2-二官能化苯，但在典型的苯炔转化中，除了其形式三键之外的位点仍然保持沉默。 3-甲硅烷基苯炔和芳基烯丙基亚砜实现了前所未有的芳炔1,2,3,5-四取代，其机理包括区域选择性芳炔插入S=O键、[3,6]-σ重排和热芳香族1,3-甲硅烷基迁移级联。
Although benzyne has been well-known to serve as a synthon that can conveniently prepare various 1,2-difunctionalized benzenes, the sites other than its formal triple bond remain silent in typical benzyne transformations. An unprecedented aryne 1,2,3,5-tetrasubstitution was realized from 3-silylbenzyne and aryl allyl sulfoxide, the mechanistic pathway of which includes a regioselective aryne insertion into the S═O bond, a [3,6]-sigmatropic rearrangement, and a thermal aromatic 1,3-silyl migration cascade.