Regio- and stereoselective hydrosilylation of alkynes with alkoxysilanes for the synthesis of β-(Z) vinylsilanes catalyzed by a dirhodium(ii)/XantPhos complex DOI
Liqun Yang,

Wenkui Lu,

Xiaoyu Wu

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(2), P. 448 - 457

Published: Nov. 27, 2023

A Rh 2 (OAc) 4 /XantPhos catalyzed regio- and stereoselective hydrosilylation of alkynes with various tertiary silanes in acetonitrile represents a straightforward highly effective strategy for the synthesis β-( Z ) vinylsilanes.

Language: Английский

Transition-metal-catalyzed enantioselective C−H silylation DOI

Yicong Ge,

Xingfen Huang, Jie Ke

et al.

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(11), P. 2898 - 2928

Published: Aug. 15, 2022

Language: Английский

Citations

60
Rhodium‐Catalyzed Dynamic Kinetic Asymmetric Hydrosilylation to Access Silicon‐Stereogenic Center DOI
Yan Zeng,

Xiao‐Jun Fang,

Ren‐He Tang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(51)

Published: Nov. 4, 2022

Abstract Strategies on the construction of enantiomerically pure silicon‐stereogenic silanes generally relies desymmetrization prochiral and symmetric substrates. However, dynamic kinetic asymmetric transformations organosilicon compounds have remained underdeveloped unforeseen owing to a lack an effective method for deracemization static silicon stereocenters. Here we report first Rh‐catalyzed intramolecular hydrosilylation (DyKAH) with “silicon‐centered” racemic hydrosilanes that enables facile preparation benzosiloles in good yields excellent enantioselectivities. The special rhodium catalyst controlled by non‐diastereopure‐type mixed phosphine‐phosphoramidite ligand axial chirality multiple stereocenters can induce enantioselectivity efficiently this novel DyKAH reaction. Density functional theory (DFT) calculations suggest amide moiety chiral plays important role facilitating S N 2 substitution chloride ion realize inversion center.

Language: Английский

Citations

45
Catalytic asymmetric silicon-carbon bond-forming transformations based on Si-H functionalization DOI Open Access
Li Li, Wei‐Sheng Huang, Zheng Xu

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(6), P. 1654 - 1687

Published: May 4, 2023

Language: Английский

Citations

38
Highly Enantioselective Construction of Multifunctional Silicon‐Stereogenic Silacycles by Asymmetric Enamine Catalysis DOI

Xue‐Xin Zhang,

Yang Gao,

Yan‐Xue Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(9)

Published: Jan. 10, 2023

We report the first highly enantioselective construction of silicon-stereocenters by asymmetric enamine catalysis. An unprecedented desymmetric intramolecular aldolization prochiral siladials was thus developed for facile access multifunctional silicon-stereogenic silacycles in high to excellent enantioselectivity. With an enal moiety, these adducts could be readily elaborated diverse synthesis compounds, and late-stage modification.

Language: Английский

Citations

36
Catalytic asymmetric synthesis of silicon-stereogenic organosilanes DOI Creative Commons
Yichen Wu,

Long Zheng,

Yan Wang

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(12), P. 3461 - 3514

Published: Oct. 19, 2023

Language: Английский

Citations

35
Chiral Silanols: Strategies and Tactics for Their Synthesis DOI

Jihui Gao,

Chuan He

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(19)

Published: Jan. 9, 2023

Silanols are valuable and important compounds, which have found widespread applications in the field of materials science, synthetic chemistry, medicinal chemistry. Although a handful approaches been developed for synthesis various silanols, access to enantioenriched silicon-stereogenic silanols remains underdeveloped. This Concept article intends summarize highlight recent advances construction endeavors encourage further research this area.

Language: Английский

Citations

33
Catalytic Asymmetric Dehydrogenative Si–H/N–H Coupling: Synthesis of Silicon-Stereogenic Silazanes DOI
Mengmeng Liu,

Yankun Xu,

Chuan He

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(21), P. 11727 - 11734

Published: May 19, 2023

Despite growing progress in the construction of silazanes, catalytic asymmetric synthesis silicon-stereogenic silazanes is significantly less explored and remains a considerable challenge. Herein, we report highly enantioselective via dehydrogenative coupling dihydrosilanes with anilines. The reaction readily produces wide range chiral bis-silazanes excellent yields stereoselectivities (up to 99% ee). Further utility this process demonstrated by polycarbosilazanes featuring configurational main chain chirality. In addition, straightforward transformation enantioenriched delivers various silane compounds stereospecific fashion, illustrating their potential utilities as synthons for novel silicon-containing functional molecules.

Language: Английский

Citations

33
Axial chirality reversal and enantioselective access to Si-stereogenic silylallene DOI Creative Commons

Chenyu Jin,

Xiaoqian He,

Shaowei Chen

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(10), P. 2956 - 2970

Published: July 18, 2023

Language: Английский

Citations

33
Organocatalytic DYKAT of Si-Stereogenic Silanes DOI Creative Commons
Hui Zhou, Roberta Properzi, Markus Leutzsch

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 4994 - 5000

Published: Feb. 24, 2023

Chiral organosilanes do not exist in nature and are therefore absent from the "chiral pool". As a consequence, synthetic approaches toward enantiopure silanes, stereogenic at silicon, rather limited. While catalytic asymmetric desymmetrization reactions of symmetric organosilicon compounds have been developed, utilization racemic silanes dynamic kinetic transformation (DYKAT) or resolution (DKR) would significantly expand breadth accessible Si-stereogenic compounds. We now report DYKAT allyl enabled by strong confined imidodiphosphorimidate (IDPi) catalysts, providing access to silyl ethers. The products this reaction easily converted into useful monohydrosilanes. propose spectroscopically experimentally supported mechanism involving epimerization catalyst-bound intermediate.

Language: Английский

Citations

32
Catalytic Kinetic Resolution of Monohydrosilanes via Rhodium‐Catalyzed Enantioselective Intramolecular Hydrosilylation DOI

Fei‐Hu Gou,

Fei Ren, Yichen Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: April 12, 2024

The catalytic access of silicon-stereogenic organosilanes remains a big challenge, and largely depends on the desymmetrization symmetric precursors with two identical substitutes attached to silicon atom. Here we report construction via kinetic resolution racemic monohydrosilanes good excellent selectivity factors. Both Si-stereogenic dihydrobenzosiloles could be efficiently accessed in one single operation Rh-catalyzed enantioselective intramolecular hydrosilylation, employing (R,R)-Et-DuPhos as optimal ligand. This protocol features mild conditions, low catalyst loading (0.1 mol % [Rh(cod)Cl]

Language: Английский

Citations

13