Copper-Catalyzed Desymmetrization of Prochiral Silanediols to Silicon-Stereogenic Silanols

Gao, Jihui1,2,3; Mai, Pei-Lin2,3; Ge, Yicong2,3,4; Yuan, Wei2,3; Li, Yingzi5; He, Chuan2,3

2022-07-01

10.1021/acscatal.2c02482

ACS Catalysis   Impact Factor & Quartile

2155-5435

Despite the growing demand for the enantioenriched silicon-stereogenic silanols in materials science, medicinal chemistry, and modern synthetic chemistry, the catalytic asymmetric synthesis of which remains a considerable challenge compared with their carbinol analogues. Herein, a copper-catalyzed desymmetrization of silanediols for the synthesis of various functionalized chiral silanols is demonstrated. The reaction features high atom economy, decent yield with excellent stereoselectivity, and H-2 as the sole byproduct. Key to the success for discrimination of the gem-diol groups in silanediol relies on an enantioselective sigma-bond metathesis process. Further straightforward elaboration of the enantioenriched silicon-stereogenic silanols delivers several interesting chiral silane scaffolds without the loss of enantiopurities.

silicon-stereogenic silanols asymmetric copper catalysis desymmetrization of silanediols dehydrogenative coupling enantioselective ?-bond metathesis

SCI ; EI

English

Corresponding

National Natural Science Foundation of China["21901104","22122102","22101120"] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Shenzhen Science and Technology Innovation Committee[JCYJ20190809142809370] ; Stable Support Plan Program of Shenzhen Natural Science Fund[20200925152450004]

Chemistry

Chemistry, Physical

WOS:000826277300001

AMER CHEMICAL SOC

20223212553882

Catalysis ; Copper ; Enantioselectivity ; Scaffolds ; Stereochemistry

Construction Equipment:405.1 ; Copper:544.1 ; 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

1.Harbin Inst Technol, Sch Chem & Chem Engn, Harbin 150080, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China
4.Leshan Normal Univ, Sch New Energy Mat & Chem, Sichuan Prov Key Lab Nat Prod & Small Mol Synth, Leshan 614000, Peoples R China
5.Univ Chinese Acad Sci, Shenzhen Inst Adv Technol, Chinese Acad Sci Shenzhen, Beijing 518055, Guangdong, Peoples R China

Gao, Jihui,Mai, Pei-Lin,Ge, Yicong,et al. Copper-Catalyzed Desymmetrization of Prochiral Silanediols to Silicon-Stereogenic Silanols[J]. ACS Catalysis,2022,12(14):8476-8483.

Gao, Jihui,Mai, Pei-Lin,Ge, Yicong,Yuan, Wei,Li, Yingzi,&He, Chuan.(2022).Copper-Catalyzed Desymmetrization of Prochiral Silanediols to Silicon-Stereogenic Silanols.ACS Catalysis,12(14),8476-8483.

Gao, Jihui,et al."Copper-Catalyzed Desymmetrization of Prochiral Silanediols to Silicon-Stereogenic Silanols".ACS Catalysis 12.14(2022):8476-8483.