Construction of Silicon-Stereogenic Center via Catalytic Asymmetric Si—H/X—H Dehydrogenative Coupling DOI Open Access

Jiayi Zhao,

Yicong Ge,

Chuan He

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(10), P. 3352 - 3352

Published: Jan. 1, 2023

Owing to its unique structure and properties, silicon-stereogenic silanes have displayed valuable application prospects in the fields of organic synthesis, functional materials biomedicine, received extensive attention from chemists.In recent years, methods for construction center been rapidly developed, especially use transition metal catalysis conduct desymmetrization prochiral silanes.Among them, asymmetric catalytic Si-H/X-H dehydrogenative coupling (Si-CADC) using dihydrosilane as substrate has become an important approach key technology center, because advantages high efficiency, atomic economy, good structural diversity enantioselectivity.According different reaction categorie products, this review will mainly summarize discuss three stages: (1) tandem strategy construct tetrasubstituted silanes, (2) intramolecular Si-H/C-H cyclic monohydrosilanes, (3) intermolecular a variety ayclic silanes.

Language: Английский

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
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
Organocatalytic enantioselective construction of Si-stereocenters: recent advances and perspectives DOI

Zhong-Tian Ye,

Zhongwei Wu,

Xue‐Xin Zhang

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(17), P. 8546 - 8562

Published: Jan. 1, 2024

Silicon-stereogenic chiral organosilanes have found increasing applications in synthetic chemistry, medicinal and materials science. In this context, various asymmetric catalytic methods been established for the diverse synthesis of silicon-stereogenic silanes. particular, organocatalysis is emerging as an important complementary tool enantioselective construction silicon-stereocenters, along with rapid development chiral-metal catalyzed protocols. Its advent provides a powerful platform to achieve functionalized structural diversity, should lead great organosilicon chemistry. Tutorial Review, we highlight these latest achievements from two aspects: desymmetrizations prochiral tetraorganosilanes dynamic kinetic transformations racemic by employing five organocatalytic activation modes. The advantages, limitations value each protocol, well opportunities still open further exploration, are also discussed.

Language: Английский

Citations

13
Copper‐Catalyzed Asymmetric Synthesis of Silicon‐Stereogenic Benzoxasiloles DOI

Wan‐Er Gan,

Yong‐Shun Wu,

Bin Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(7)

Published: Jan. 5, 2024

Abstract A Cu‐catalyzed asymmetric synthesis of silicon‐stereogenic benzoxasiloles has been realized via intramolecular Si−O coupling [2‐(hydroxymethyl)phenyl]silanes. Cu(I)/difluorphos is found to be an efficient catalytic system for enantioselective Si−C bond cleavage and formation. In addition, kinetic resolution racemic substituted [2‐(hydroxymethyl)phenyl]silanes using Cu(I)/ PyrOx (pyridine‐oxazoline ligands) as the developed afford carbon‐ benzoxasiloles. Ring‐opening reactions chiral with organolithiums Grignard reagents yield various enantioenriched functionalized tetraorganosilanes.

Language: Английский

Citations

12
Copper-catalyzed intermolecular Regio- and Enantioselective Hydrosilylation of Alkenes with Prochiral Silanes DOI Creative Commons
Xiaoyan Zhu,

Wenyu Gao,

Jian‐Lin Xu

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 3, 2025

This study presents a copper-catalyzed, substrate-controlled regio- and enantioselective intermolecular hydrosilylation method capable of accommodating broad scope alkenes prochiral silanes. The approach offers an efficient versatile pathway to generate enantioenriched linear branched alkyl-substituted Si-stereogenic Key features this reaction include mild conditions, simple catalytic systems, compatibility with diverse substrates, high yields enantioselectivities. While methods create chiral carbon centers stereochemically defined silicon have been developed, the ability both simultaneously would be value. Here authors present substratecontrolled

Language: Английский

Citations

1
Divergent Synthesis of Silacycles by Ligand-Controlled Rhodium-Catalyzed Annulation of (2-Hydrosilylaryl)acetylenes DOI

Kazuto Fuji,

Kyohei Kawashima, Toshifumi Mori

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

This study demonstrates the rhodium-catalyzed divergent synthesis of 5-, 5,6-, and 8-membered silacyclic compounds, such as benzosilole, silolosiline, disilocine, from (2-hydrosilylaryl)acetylenes. To achieve high product selectivity, intra- intermolecular reactions are controlled by tuning mono- bidentate phosphine ligands on rhodium catalyst precursor. Deuterium labeling experiments computational studies reveal that annulation reaction proceeds via hydride transfer to alkyne moiety.

Language: Английский

Citations

1