Rhodium‐Catalyzed Enantioselective Formal [4+1] Cyclization of Benzyl Alcohols and Benzaldimines: Facile Access to Silicon‐Stereogenic Heterocycles DOI

Bing-Xue Shen,

Deng Pan,

Wanying Xie

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 8, 2023

The carbon-to-silicon switch in formation of bioactive sila-heterocycles with a silicon-stereogenic center has garnered significant interest drug discovery. However, metal-catalyzed synthesis such scaffolds is still its infancy. Herein, rhodium-catalyzed enantioselective formal [4+1] cyclization benzyl alcohols and benzaldimines been realized by difunctionalization secondary silane reagent, affording chiral-at-silicon cyclic silyl ethers sila-isoindolines, respectively. Mechanistic studies reveal dual role the rhodium-hydride catalyst. coupling system proceeds via enantio-determining dehydrogenative OH silylation alcohol or hydrosilylation imine to give an enantioenriched ether silazane intermediate, same rhodium catalyst also enables subsequent intramolecular cyclative C-H directed pendent Si-H group. Experimental DFT have conducted explore mechanism bond alcohol, where Si-O reductive elimination from Rh(III) hydride intermediate established as enantiodetermining step.

Language: Английский

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions DOI
Chen‐Xu Liu,

Si‐Yong Yin,

Fangnuo Zhao

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Language: Английский

Citations

124
Catalytic Asymmetric Synthesis of Silicon‐Stereogenic Dihydrodibenzosilines: Silicon Central‐to‐Axial Chirality Relay DOI

Yonghong Guo,

Mengmeng Liu,

Xujiang Zhu

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(25), P. 13887 - 13891

Published: April 8, 2021

Abstract A Rh‐catalyzed asymmetric synthesis of silicon‐stereogenic dihydrodibenzosilines featuring axially chiral 6‐membered bridged biaryls is demonstrated. In the presence a Rh I catalyst with diphosphine ligand, wide range containing both silicon‐central and axial chiralities are conveniently constructed in excellent enantioselectivities via dehydrogenative C(sp 3 )−H silylation. Absolute configuration analysis by single‐crystal X‐ray structures revealed novel silicon central‐to‐axial chirality relay phenomenon, which we believe will inspire further research field catalysis chiroptical materials.

Language: Английский

Citations

116
Enantioselective C–H Functionalization toward Silicon-Stereogenic Silanes DOI
Chuan He, Wei Yuan

Synthesis, Journal Year: 2022, Volume and Issue: 54(08), P. 1939 - 1950

Published: Jan. 3, 2022

Abstract In recent years, transition-metal-catalyzed enantioselective C–H bond functionalization has emerged as a powerful and attractive synthetic approach to access silicon-stereogenic centers, which provides impetus for the innovation of chiral organosilicon chemistry. This short review summarizes advances in construction silanes via functionalization. We endeavor highlight great potential this methodology hope that will shed light on new perspectives inspire further research emerging area. 1 Introduction 2 Enantioselective Functionalization Induced by Oxidative Addition­ an Aryl-OTf Bond 3 Silacyclobutane 4 Directing-Group-Assisted 5 Dehydrogenative C–H/Si–H Coupling 5.1 C(sp2)–H Silylation 5.2 C(sp3)–H 6 Summary Outlook

Language: Английский

Citations

93
Construction of Si‐Stereogenic Silanes through C−H Activation Approach DOI

Long Zheng,

Xiao‐Xue Nie,

Yichen Wu

et al.

European Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 2021(44), P. 6006 - 6014

Published: Sept. 21, 2021

Abstract The asymmetric synthesis of Si‐stereogenic silanes has attracted great attention due to the increasing values Si‐containing functional molecules in synthetic chemistry, medicinal and material chemistry. Merging organosilicon chemistry with transition‐metal‐catalyzed C−H approach led rich sets new reactions holding values. This Minireview aims summarize advances construction through activation approach.

Language: Английский

Citations

63
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 hydride enabled enantioselective intermolecular C–H silylation to access acyclic stereogenic Si–H DOI Creative Commons
Kun An,

Wenpeng Ma,

Lichuan Liu

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Feb. 14, 2022

The tremendous success of stereogenic carbon compounds has never ceased to inspire researchers explore the potentials silicon compounds. Intermolecular C-H silylation thus represents most versatile and straightforward strategy construct C-Si bonds, however, its enantioselective variant been scarcely reported date. Herein we report a protocol that allows for intermolecular bond silylation, leading construction wide array acyclic Si-H under simple mild reaction conditions. Key is (1) substrate design prevents self-reaction prochiral silane (2) employment more reactive rhodium hydride ([Rh]-H) catalyst as opposed commonly used chloride ([Rh]-Cl) catalyst. This work unveils opportunities in converting arenes into value-added

Language: Английский

Citations

59
Enantioselective Synthesis of Spirosilabicyclohexenes by Asymmetric Dual Ring Expansion of Spirosilabicyclobutane with Alkynes DOI
Hua Chen,

Ju Peng,

Qinjiao Pang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(48)

Published: Oct. 7, 2022

Silaspiranes have attracted particular attention due to their chiral spiro-silicon center, which serves as an ideal carbon isostere and can endow spiro-analogs with distinct properties. Distinct from previously reported cyclization or cycloaddition strategies form 5/5-silaspiranes, we report herein the asymmetric dual ring expansion of spirosilabicyclobutanes alkynes synthesize axially spirosilabicyclohexenes bearing a novel 6/6-silaspirane framework. DFT (density functional theory) calculations provide deep insight into origin high enantioselectivity controlled by sterically demanding binaphthyl phosphoramidite ligand. Preliminary studies chiroptical properties indicate that one spirosilabicyclohexene analogs exhibit fluorescence emission, Cotton effects CPL (circularly polarized luminescence) activity.

Language: Английский

Citations

50
Synthesis of Si‐Stereogenic Silanols by Catalytic Asymmetric Hydrolytic Oxidation DOI
Wei Yuan,

Xujiang Zhu,

Yankun Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 26, 2022

Despite growing progress in the construction of chiral organosilicon compounds, catalytic asymmetric synthesis silicon-stereogenic silanols is less explored and remains a considerable challenge. Herein, we report first enantioselective by hydrolytic oxidation dihydrosilanes. This practical procedure features ambient reaction conditions, high atom economy, good functional-group compatibility, H2 as only by-product, produces wide range valuable bis-silanols decent yields with excellent chemo- stereoselectivity.

Language: Английский

Citations

48
Ring Expansion of Silacyclobutanes with Allenoates to Selectively Construct 2- or 3-(E)-Enoate-Substituted Silacyclohexenes DOI
Xiaoxiao Tang, Yan Zhang,

Yulang Tang

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(9), P. 5185 - 5196

Published: April 15, 2022

Silacycle is one of the most essential core frameworks in silicon-containing functional molecules. However, structural diversity silacycles has been largely limited due to lack general synthetic methods. Here, we report an efficient synthesis exo-cyclic enoate-substituted silacyclohexenes by ring expansion silacyclobutanes with allenoates. The reaction proceeds two regioselectivities during Si–C bond insertion. In presence Pd/PR3 catalyst, unsubstituted allenoates undergo β, γ-insertion form a Si–Cβ bond, giving 2-(E)-enoate-substituted silacyclohexenes. this pathway, chiral phosphoramidite ligand used construct stereogenic silicon center enantioselectively. second PtCl2 α-substituted γ, β-insertion Si–Cγ leading 3-(E)-enoate-substituted control experiments and density theory calculations have performed understand regio- stereochemical outcome both Pd- Pt-catalyzed reactions.

Language: Английский

Citations

46
Copper-Catalyzed Desymmetrization of Prochiral Silanediols to Silicon-Stereogenic Silanols DOI
Jihui Gao,

Pei-Lin Mai,

Yicong Ge

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(14), P. 8476 - 8483

Published: July 1, 2022

Despite the growing demand for enantioenriched silicon-stereogenic silanols in materials science, medicinal chemistry, and modern synthetic catalytic asymmetric synthesis of which remains a considerable challenge compared with their carbinol analogues. Herein, copper-catalyzed desymmetrization silanediols various functionalized chiral is demonstrated. The reaction features high atom economy, decent yield excellent stereoselectivity, H2 as sole byproduct. Key to success discrimination gem-diol groups silanediol relies on an enantioselective σ-bond metathesis process. Further straightforward elaboration delivers several interesting silane scaffolds without loss enantiopurities.

Language: Английский

Citations

46