Enantioselective Synthesis of Axially Chiral Silacyclohexylidene Oxime Ethers by Chiral Phosphoric Acid Catalysis DOI
Xiyu Wang, Xingang Xie, Zhongwei Wu

et al.

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Abstract The first asymmetric condensation of prochiral silacyclohexanones with hydroxylamines by chiral phosphoric acid catalysis has been developed, which provides a facile and straightforward protocol for the enantioselective construction valuable axially silacyclohexylidene oxime ethers that are otherwise inaccessible. Notably, this constitutes rare example accessing silacycles featuring axial chirality.

Language: Английский

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

33
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
Lewis Base-Catalyzed Dynamic Kinetic Asymmetric Transformation of Racemic Chlorosilanes en Route to Si-Stereogenic Silylethers DOI

Tianbao Hu,

Yan Zhang,

Wanshu Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23092 - 23102

Published: Aug. 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.

Language: Английский

Citations

9
Enantioselective Copper‐Catalyzed Sequential Hydrosilylation of Arylmethylenecyclopropanes DOI
Bin Fu, Lianghua Wang, Kexin Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 18, 2024

Abstract Despite impressive advances in the construction of enantioenriched silacarbocycles featuring silicon‐stereogenic centers via a selection well‐defined sila‐synthons, development more convenient and economic method with readily available starting materials is significantly less explored remains considerable challenge. Herein, we report first example copper‐catalyzed sequential hydrosilylation accessible methylenecyclopropanes (MCPs) primary silanes, affording an efficient route to wide range chiral silacyclopentanes bearing consecutive silicon‐ carbon‐stereogenic excellent enantio‐ diastereoselectivities (generally ≥98 % ee, >25 : 1 dr). Mechanistic studies reveal that these reactions combine intermolecular ring‐opening aryl MCPs intramolecular asymmetric resultant Z / E mixture homoallylic silanes.

Language: Английский

Citations

7
Divergent Synthesis of Enantioenriched Silicon‐Stereogenic Benzyl−, Vinyl− and Borylsilanes via Asymmetric Aryl to Alkyl 1,5‐Palladium Migration DOI
Yufeng Shi, Ying Qin, Zhong‐Qiu Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: July 30, 2024

Functionalization of Si-bound methyl group provides an efficient access to diverse organosilanes. However, the asymmetric construction silicon-stereogenic architectures by functionalization has not yet been described despite recent significant progress in producing chiral silicon. Herein, we disclosed enantioselective silylmethyl involving aryl alkyl 1,5-palladium migration naphthalenes possessing enantioenriched stereogenic silicon center, which are inaccessible before. It is worthy note that realization induction at step metal itself remains challenging. Our study constitutes first reaction. The key success discovery and fine-tuning different substituents α,α,α,α-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL)-based phosphoramidites, ensure enantioselectivity desired reactivity.

Language: Английский

Citations

5
Rh-Catalyzed Enantioselective Desymmetric Hydrogenation of α-Acetamido-1,3-indanediones Using Ether-Bridged Biphenyl Diphosphine Ligands DOI
Yunnan Xu, Yicong Luo,

Jianxun Ye

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21176 - 21182

Published: Aug. 23, 2023

Novel axially chiral biphenyl diphosphine ligands Enm-BridgePhos, bearing an ether chain bridge at the 5,5'-position of backbone, have been developed and successfully applied in Rh-catalyzed enantioselective desymmetric hydrogenation α-acetamido-1,3-indanediones, providing α-acetamido-β-hydroxybenzocyclic pentones high yields (up to 97%) with excellent enantioselectivities 99% ee). The reaction could be carried out on a gram scale, corresponding products were used as vital intermediates for synthesis analogues spirobenzylisoquinoline alkaloids. Both crystal structure analysis DFT calculations revealed that large dihedral angle Enm-BridgePhos-Rh complexes is highly related enantioselectivities.

Language: Английский

Citations

11
Design and Synthesis of Chiral Spiro Monophosphinites with a 3-Oxo-1,1′-spirobiindane Scaffold and Their Application in Rhodium-Catalyzed Asymmetric Hydrogenation of Dehydroamino Acid Esters DOI
Zhi Huang, P. Hu, Jian‐Hua Xie

et al.

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

Published: April 15, 2025

A new class of chiral spiro monophosphinites, based on a unique non-C2-symmetric 3-oxo-1,1'-spirobiindane scaffold featuring large dihedral angle, has been effectively designed and synthesized. From readily accessible resources, these monophosphinites were synthesized via eight steps in 16-32% yields. Their excellent performance the rhodium-catalyzed asymmetric hydrogenation β-dehydroamino acid esters underscores critical impact angle enhancing activity enantioselectivity.

Language: Английский

Citations

0
Development of a One-Step Synthesis of oxa-Spirocyclic Diphosphine Ligands Driven by Their Application in the Industrial Synthesis of Sacubitril DOI
Gen‐Qiang Chen,

Renwei Xiao,

Xiaobing Ding

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(14), P. 2811 - 2816

Published: Jan. 16, 2024

Herein we have developed a highly practical and efficient one-step coupling protocol for the synthesis of chiral spiro diphosphine ligands, especially oxa-spiro ligands O-SDP, which showed excellent reactivity diastereoselectivity in asymmetric hydrogenation key intermediate Sacubitril. It should be noted that could operated on kilogram scale, resulting ruthenium catalyst O-SDP hydrogenate Sacubitril an industrial scale.

Language: Английский

Citations

3
Bis-indole chiral architectures for asymmetric catalysis DOI Creative Commons
Junshan Lai, Benjamin List, Jolene P. Reid

et al.

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

Published: April 17, 2025

Abstract Chiral scaffolds are essential to the advancement of asymmetric synthesis, yet development privileged motifs that more effectively communicate asymmetry constitutes a grand challenge for chemists. Here we describe method using confined chiral Brønsted acid catalyst combine two inexpensive and widely available materials—indole acetone—into class C₂-symmetric, spirocyclic compounds called SPINDOLE. SPINDOLEs extend versatility established frameworks by offering greater flexibility ease synthesis. The resulting can be readily modified create diverse structures excel in promoting highly selective reactions such as hydrogenation, allylic alkylation, hydroboration, Michael addition. This work introduces powerful strategy advancing catalysis, enabling creation versatile with broad synthetic potential.

Language: Английский

Citations

0