1393834-75-7Relevant academic research and scientific papers
Benzyne 1,2,4-Trisubstitution and Dearomative 1,2,4-Trifunctionalization
Chen, Zhonghong,Dai, Liang,Lan, Yu,Li, Lianggui,Li, Yang,Shan, Chunhui,Shi, Jiarong,Tan, Min
supporting information, p. 10530 - 10536 (2021/07/28)
Both 1,2,4-trisubstitution and dearomative 1,2,4-trifunctionalization of benzyne have been accomplished from sulfoxides bearing a penta-2,4-dien-1-yl moiety. These cascade transformations proceed through a benzyne insertion into the S═O bond and an uncommon regiospecific anionic [4,5]-sigmatropic rearrangement, furnishing a C-O, C-S, and C-C bond on the C1-, C2-, and C4-position of a benzene ring, respectively. This study showcases new cascade benzyne reaction modes involving both distal C-H bond functionalization and dearomatization.
Aryne 1,2,3,5-Tetrasubstitution Enabled by 3-Silylaryne and Allyl Sulfoxide via an Aromatic 1,3-Silyl Migration
Shi, Jiarong,Li, Lianggui,Shan, Chunhui,Wang, Junli,Chen, Zhonghong,Gu, Rongrong,He, Jia,Tan, Min,Lan, Yu,Li, Yang
supporting information, p. 2178 - 2184 (2021/02/16)
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 SO bond, a [3,6]-sigmatropic rearrangement, and a thermal aromatic 1,3-silyl migration cascade.
Steric effects compete with aryne distortion to control regioselectivities of nucleophilic additions to 3-silylarynes
Bronner, Sarah M.,MacKey, Joel L.,Houk,Garg, Neil K.
, p. 13966 - 13969 (2012/10/29)
We report an experimental and computational study of 3-silylarynes. The addition of nucleophiles yield ortho-substituted products as a result of aryne distortion, but meta-substituted products form predominately when the nucleophile is large. Computations correctly predict the preferred site of attack observed in both nucleophilic addition and cycloaddition experiments. Nucleophilic additions to 3-tert-butylbenzyne, which is not significantly distorted, give meta-substituted products.
