Revisiting the Mg/TMSCl/Dipolar Solvent System for Dearomatic Silylation of Aryl Carbonyl Compounds: Substrate Scope, Transformations, and Mechanistic Studies

Li, Nan-Nan1; Li, Meng1; Gao, Jia-Ni1; Zhang, Zhong1; Xie, Jian-Bo1,2

2022-07-01

10.1021/acs.joc.2c01178

JOURNAL OF ORGANIC CHEMISTRY   影响因子和分区

0022-3263

1520-6904

Dearomatic silylation of arene derivatives is an intriguing synthetic target, which represents an elegant extension of Birch reduction and produces silylated cyclohexene derivatives with great potential of further transformation. Herein, we report a systematic study on dearomatic silylation of aryl carbonyl compounds with Mg and the TMSCl/NMP adduct. The protocol displays a wide range of substrate scope, including alkyl aryl ketones, aromatic amides, benzonitriles, tert-butyl benzoates, and even 2,2 & PRIME;-bipyridines. Synthetic utility is demonstrated using the products as versatile substrate in various transformations. The detailed mechanism is presented with both control experimental analyses and theoretical calculations. An unusual five-coordinated silicon dianion intermediate is first proposed and described here. The selectivity is influenced by the relative rates of single electron reductions (the TMSCl/NMP adduct versus the substrate) and the steric effects.

SCI ; EI

英语

通讯

Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; [21702164]

Chemistry

Chemistry, Organic

WOS:000835501500001

AMER CHEMICAL SOC

20223412607018

Amides ; Aromatic hydrocarbons ; Ketones

Organic Compounds:804.1

CHEMISTRY

Web of Science

1.Northwest A&F Univ, Coll Chem Pharm, Shaanxi Key Lab Nat Prod & Chem Biol, Yangling 712100, Peoples R China
2.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China

Li, Nan-Nan,Li, Meng,Gao, Jia-Ni,et al. Revisiting the Mg/TMSCl/Dipolar Solvent System for Dearomatic Silylation of Aryl Carbonyl Compounds: Substrate Scope, Transformations, and Mechanistic Studies[J]. JOURNAL OF ORGANIC CHEMISTRY,2022,87:10876-10889.

Li, Nan-Nan,Li, Meng,Gao, Jia-Ni,Zhang, Zhong,&Xie, Jian-Bo.(2022).Revisiting the Mg/TMSCl/Dipolar Solvent System for Dearomatic Silylation of Aryl Carbonyl Compounds: Substrate Scope, Transformations, and Mechanistic Studies.JOURNAL OF ORGANIC CHEMISTRY,87,10876-10889.

Li, Nan-Nan,et al."Revisiting the Mg/TMSCl/Dipolar Solvent System for Dearomatic Silylation of Aryl Carbonyl Compounds: Substrate Scope, Transformations, and Mechanistic Studies".JOURNAL OF ORGANIC CHEMISTRY 87(2022):10876-10889.