Catalytic Enantioselective Dehydrogenative Si-O Coupling to Access Chiroptical Silicon-Stereogenic Siloxanes and Alkoxysilanes

Jiefeng Zhu; Shuyou Chen; Chuan He

doi:10.1021/jacs.1c01106

Catalytic Enantioselective Dehydrogenative Si-O Coupling to Access Chiroptical Silicon-Stereogenic Siloxanes and Alkoxysilanes

J Am Chem Soc. 2021 Apr 14;143(14):5301-5307. doi: 10.1021/jacs.1c01106. Epub 2021 Apr 1.

Authors

Jiefeng Zhu^{1

2}, Shuyou Chen², Chuan He²

Affiliations

¹ School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150080, China.
² Shenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.

PMID: 33792300
DOI: 10.1021/jacs.1c01106

Abstract

A rhodium-catalyzed enantioselective construction of triorgano-substituted silicon-stereogenic siloxanes and alkoxysilanes is developed. This process undergoes a direct intermolecular dehydrogenative Si-O coupling between dihydrosilanes with silanols or alocohols, giving access to a variety of highly functionalized chiral siloxanes and alkoxysilanes in decent yields with excellent stereocontrol, that significantly expand the chemical space of the silicon-centered chiral molecules. Further utility of this process was illustrated by the construction of CPL-active (circularly polarized luminescence) silicon-stereogenic alkoxysilane small organic molecules. Optically pure bis-alkoxysilane containing two silicon-stereogenic centers and three pyrene groups displayed a remarkable g_lum value with a high fluorescence quantum efficiency (g_lum = 0.011, Φ_F = 0.55), which could have great potential application prospects in chiral organic optoelectronic materials.