Forging C−heteroatom bonds by transition-metal-catalyzed enantioselective C–H functionalization

Chem, Год журнала: 2021, Номер 8(2), С. 384 - 413

Опубликована: Дек. 17, 2021

Язык: Английский

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Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Год журнала: 2023, Номер 123(16), С. 10079 - 10134

Опубликована: Авг. 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.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(25), С. 13887 - 13891

Опубликована: Апрель 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.

Язык: Английский

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Enantioselective C–H Functionalization toward Silicon-Stereogenic Silanes

Synthesis, Год журнала: 2022, Номер 54(08), С. 1939 - 1950

Опубликована: Янв. 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

Язык: Английский

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Catalytic Enantioselective Dehydrogenative Si–O Coupling to Access Chiroptical Silicon-Stereogenic Siloxanes and Alkoxysilanes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(14), С. 5301 - 5307

Опубликована: Апрель 1, 2021

A rhodium-catalyzed enantioselective construction of triorgano-substituted silicon-stereogenic siloxanes and alkoxysilanes is developed. This process undergoes a direct intermolecular dehydrogenative Si–O coupling between dihydrosilanes with silanols or alocohols, giving access to variety highly functionalized chiral in decent yields excellent stereocontrol, that significantly expand the chemical space silicon-centered molecules. Further utility this was illustrated by CPL-active (circularly polarized luminescence) alkoxysilane small organic Optically pure bis-alkoxysilane containing two centers three pyrene groups displayed remarkable glum value high fluorescence quantum efficiency (glum = 0.011, ΦF 0.55), which could have great potential application prospects optoelectronic materials.

Язык: Английский

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Enantioselective Synthesis of Silicon‐Stereogenic Monohydrosilanes by Rhodium‐Catalyzed Intramolecular Hydrosilylation

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(1)

Опубликована: Ноя. 3, 2021

Enantiopure monohydrosilanes are versatile chiral reagents for alcohol resolution and mechanistic investigation. Herein, we have demonstrated the asymmetric synthesis of via an intramolecular hydrosilylation strategy. This protocol is suitable five- six-membered cyclic monohydrosilanes, including a class oxasilacycles, with excellent diastereo-, regio-, enantioselectivities. Notably, catalyst loading could be reduced to 0.1 mol % which makes this one most efficient methods access monohydrosilanes. Mechanistic studies DFT calculations indicate Rh-catalyzed reaction might proceed Chalk-Harrod mechanism, enantio-determining step was predicted oxidative addition Si-H bond.

Язык: Английский

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A Combined Computational and Experimental Study of Rh-Catalyzed C–H Silylation with Silacyclobutanes: Insights Leading to a More Efficient Catalyst System

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(9), С. 3571 - 3582

Опубликована: Фев. 23, 2021

The study of new C–H silylation reagents and reactions remains an important topic. We reported that under Rh catalysis, silacyclobutanes (SCBs) for the first time were able to react with C(sp2)–H C(sp3)–H bonds, however underlying reasons such a reactivity not understood. Through this combined computational experimental on SCBs, we only depict reaction pathway fully accounts all findings but also streamline more efficient catalyst significantly improves rates yields. Our key include: (1) active catalytic species is [Rh]–H as opposed previously proposed [Rh]–Cl; (2) generated via reductive elimination/β-hydride (β-H) elimination sequence, endocyclic β-H elimination; (3) regio- enantio-determining steps are identified; (4) same importance, discretely synthesized shown be catalyst. This work suggests [Rh]–H/diphosphine system should find further applications in silylations involving SCBs.

Язык: Английский

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Nickel(0)‐Catalyzed Asymmetric Ring Expansion Toward Enantioenriched Silicon‐Stereogenic Benzosiloles

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(49), С. 25723 - 25728

Опубликована: Сен. 30, 2021

The development of a straightforward strategy to obtain enantioenriched silicon-stereogenic benzosiloles remains challenging yet appealing synthesis venture due their potential future application in chiral electronic and optoelectronic devices. In this context, all the existing methods rely on Rh-catalyzed systems are somewhat limited scope. Herein, we disclose first Ni0 -catalyzed ring expansion process that enables preparation possessing tetraorganosilicon stereocenters excellent yields enantioselectivities. presented catalysis is further applied asymmetric bis-silicon-bridged π-extended systems. Preliminary studies reveal such compounds exhibit fluorescence emission, Cotton effects circularly polarized luminescence (CPL) activity.

Язык: Английский

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

European Journal of Organic Chemistry, Год журнала: 2021, Номер 2021(44), С. 6006 - 6014

Опубликована: Сен. 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.

Язык: Английский

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Catalytic Enantioselective Construction of Chiroptical Boron-Stereogenic Compounds

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(39), С. 16302 - 16310

Опубликована: Сен. 27, 2021

The construction of main group heteroatom-stereogenic compounds is great importance due to their intriguing chemical, physical, biological, and stereoelectronic properties. Despite that organoboron are widely used in organic chemistry, the creation a tetrahedral boron-stereogenic center one enantiomeric form remains highly challenging. Given labile nature ligands attached tetracoordinate boron atom, only handful enantioenriched have been reported via resolution or chiral substrate-induced diastereoselective approach. To date catalytic asymmetric synthesis has remained unknown. Here, we demonstrate first enantioselective an copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. This CuAAC reaction not gives access wide range novel functionalized heterocycles high yields with good excellent enantioselectivities but also produces optically active terminal alkyne triazole moieties various potential application prospects. Further transformation delivers several complex heterocyclic entities bearing centers without loss enantiopurity. Moreover, X-ray structure, barrier racemization, HOMO/LUMO gap selected investigated. Notably, these N,N π-conjugated exhibit bright fluorescence. optical properties, including circular dichroism, quantum yield, polarized luminescence spectroscopies, examined. These features expand chemical space chiroptical boron-based dye platform, which could applications optoelectronic materials.

Язык: Английский

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