Organocatalytic Si-C_Aryl Bond Functionalization-Enabled Atroposelective Synthesis of Axially Chiral Biaryl Siloxanes

Wu, Ming; Chen, Yi-Wei; Lu, Qian; Wang, Yong-Bin; Cheng, Jun Kee; Yu, Peiyuan; Tan, Bin

2023-09-11

10.1021/jacs.3c07839

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

Chiral organosilanes are valuable chemical entities in the development of functional organic materials, asymmetric catalysis, and medicinal chemistry. As an important strategy for constructing chiral organosilanes, the asymmetric functionalization of the Si-C-Aryl bond typically relies on transition-metal catalysis. Herein, we present an efficient method for atroposelective synthesis of biaryl siloxane atropisomers via organocatalytic Si-C bond functionalization of dinaphthosiloles with silanol nucleophiles. The reaction proceeds through an asymmetric protonation and simultaneous Si-C bond cleavage/silanolysis sequence in the presence of a newly developed chiral Bronsted acid catalyst. The versatile nature of the Si-C bond streamlines the derivatization of axially chiral products into other functional atropisomers, thereby expanding the applicability of this method.

SCI ; EI ; IC ; CCR

英语

NI论文

第一 ; 通讯

National Natural Science Foundation of China["21825105","22231004","22371113"] ; National Key R&D Program of China["2022YFA1503703","2021YFF0701604"] ; Guangdong Innovative Program[2019BT02Y335] ; Shenzhen Science and Technology Program["KQTD20210811090112004","JCYJ20210324104212035","JCYJ20220818100604009","JCYJ20210324120205016"]

Chemistry

Chemistry, Multidisciplinary

WOS:001069241700001

AMER CHEMICAL SOC

20234014833027

Bromine compounds ; Chemical bonds ; Silicon ; Silicon compounds ; Stereochemistry ; Transition metals

Metallurgy and Metallography:531 ; Nonferrous Metals and Alloys excluding Alkali and Alkaline Earth Metals:549.3 ; Chemistry:801 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2

Web of Science

Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China

Wu, Ming,Chen, Yi-Wei,Lu, Qian,et al. Organocatalytic Si-C_Aryl Bond Functionalization-Enabled Atroposelective Synthesis of Axially Chiral Biaryl Siloxanes[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023,145(37):20646-20654.

Wu, Ming.,Chen, Yi-Wei.,Lu, Qian.,Wang, Yong-Bin.,Cheng, Jun Kee.,...&Tan, Bin.(2023).Organocatalytic Si-C_Aryl Bond Functionalization-Enabled Atroposelective Synthesis of Axially Chiral Biaryl Siloxanes.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,145(37),20646-20654.

Wu, Ming,et al."Organocatalytic Si-C_Aryl Bond Functionalization-Enabled Atroposelective Synthesis of Axially Chiral Biaryl Siloxanes".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 145.37(2023):20646-20654.