Lewis Base-Catalyzed Dynamic Kinetic Asymmetric Transformation of Racemic Chlorosilanes en Route to Si-Stereogenic Silylethers DOI

Tianbao Hu,

Yan Zhang,

Wanshu Wang

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(33), С. 23092 - 23102

Опубликована: Авг. 7, 2024

Enantiopure Si-stereogenic organosilanes are highly valued in the fields of organic synthesis, development advanced materials, and drug discovery. However, they not naturally occurring, their synthesis has been largely confined to resolution racemic silanes or desymmetrization symmetric silanes. In contrast, dynamic kinetic asymmetric transformation (DYKAT) offers a mechanistically distinct approach would broaden accessibility an enantioconvergent manner. this study, we report Lewis base-catalyzed DYKAT chlorosilanes. The chiral isothiourea catalyst, (S)-benzotetramisole, facilitates silyletherification with phenols, yielding (R)-silylethers good yields high enantioselectivity (27 examples, up 86% yield, 98:2 er). Kinetic analysis, control experiments, DFT calculations suggest that two-catalyst-bound pentacoordinate silicate is responsible for Si-configurational epimerization ion-paired tetracoordinated silicon intermediates.

Язык: Английский

Lewis Base-Catalyzed Dynamic Kinetic Asymmetric Transformation of Racemic Chlorosilanes en Route to Si-Stereogenic Silylethers DOI

Tianbao Hu,

Yan Zhang,

Wanshu Wang

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(33), С. 23092 - 23102

Опубликована: Авг. 7, 2024

Enantiopure Si-stereogenic organosilanes are highly valued in the fields of organic synthesis, development advanced materials, and drug discovery. However, they not naturally occurring, their synthesis has been largely confined to resolution racemic silanes or desymmetrization symmetric silanes. In contrast, dynamic kinetic asymmetric transformation (DYKAT) offers a mechanistically distinct approach would broaden accessibility an enantioconvergent manner. this study, we report Lewis base-catalyzed DYKAT chlorosilanes. The chiral isothiourea catalyst, (S)-benzotetramisole, facilitates silyletherification with phenols, yielding (R)-silylethers good yields high enantioselectivity (27 examples, up 86% yield, 98:2 er). Kinetic analysis, control experiments, DFT calculations suggest that two-catalyst-bound pentacoordinate silicate is responsible for Si-configurational epimerization ion-paired tetracoordinated silicon intermediates.

Язык: Английский

Процитировано

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