N-Heterocyclic carbenes as privileged ligands for nickel-catalysed alkene functionalisation

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(9), P. 2946 - 2991

Published: Jan. 1, 2023

This review discusses the applications of N-heterocyclic carbene ligands and their influence on reactivity selectivity Ni-catalysed alkene functionalisations.

Language: Английский

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Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(85), P. 12669 - 12684

Published: Jan. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Language: Английский

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Ligand-Controlled Cobalt-Catalyzed Regio-, Enantio-, and Diastereoselective Oxyheterocyclic Alkene Hydroalkylation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3405 - 3415

Published: Jan. 29, 2024

Metal-hydride-catalyzed alkene hydroalkylation has been developed as an efficient method for C(sp

Language: Английский

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Enantio‐ and Regioselective NiH‐Catalyzed Reductive Hydroarylation of Vinylarenes with Aryl Iodides

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(48), P. 21530 - 21534

Published: Aug. 28, 2020

Abstract A highly enantio‐ and regioselective hydroarylation process of vinylarenes with aryl halides has been developed using a NiH catalyst new chiral bis imidazoline ligand. broad range structurally diverse, enantioenriched 1,1‐diarylalkanes, structure found in number biologically active molecules, have obtained excellent yields enantioselectivities under extremely mild conditions.

Language: Английский

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Low-Coordinate NHC–Zinc Hydride Complexes Catalyze Alkyne C–H Borylation and Hydroboration Using Pinacolborane

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(6), P. 5760 - 5771

Published: May 15, 2019

Organozinc compounds containing sp, sp2, and sp3 C–Zn moieties undergo transmetalation with pinacolborane (HBPin) to produce Zn–H species organoboronate esters (RBPin). This Zn–C/H–B metathesis step is key enabling zinc-catalyzed borylation reactions, it used in this work develop both terminal alkyne C–H internal hydroboration. These two conversions can be combined one pot achieve the conversion of alkynes 1,1-diborylated alkenes without isolation sensitive (to protodeboronation) alkynyl boronate ester intermediates. Mechanistic studies involving intermediates, stoichiometric experiments, DFT calculations all support mechanisms organozinc that HBPin. Furthermore, hydroboration proceed via a hydrozincation step, which does not require any exogenous catalyst contrast previously reported hydrozincations. Bulky N-heterocyclic carbenes (NHCs) are for effective catalysis as NHC steric bulk enhances stability NHC–Zn present during provides access low-coordinate (NHC)Zn–H cations electrophilic yet Brønsted basic. an alternative approach synthetically desirable pinacol–organoboronate using earth-abundant metal-based catalysts.

Language: Английский

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Ligand-Enabled Ni-Catalyzed Enantioselective Hydroarylation of Styrenes and 1,3-Dienes with Arylboronic Acids

CCS Chemistry, Journal Year: 2019, Volume and Issue: 1(4), P. 328 - 334

Published: Oct. 1, 2019

We report an enantioselective hydroarylation reaction of styrenes and 1,3-dienes with arylboronic acids catalyzed by nickel complexes bearing chiral spiro aminophosphine ligands. The serve...

Language: Английский

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Iron-Catalyzed Regiodivergent Alkyne Hydrosilylation

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(39), P. 16894 - 16902

Published: Sept. 18, 2020

Although tremendous effort has been devoted to the development of methods for iron catalysis, few catalysts reported date exhibit clear superiority other metal catalysts, and mechanisms most catalysis remain unclear. Herein, we report that complexes bearing 2,9-diaryl-1,10-phenanthroline ligands not only unprecedented catalytic activity but also unusual ligand-controlled divergent regioselectivity in hydrosilylation reactions various alkynes. The protocol described herein provides a highly efficient method preparing useful di- trisubstituted olefins on relatively large scale under mild conditions, its use markedly improved synthetic efficiency number bioactive compounds. Mechanistic studies based control experiments density functional theory calculations were performed understand pathway observed regioselectivity.

Language: Английский

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Ligand-promoted cobalt-catalyzed radical hydroamination of alkenes

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: Feb. 7, 2020

Highly regio- and enantioselective intermolecular hydroamination of alkenes is a challenging process potentially leading to valuable chiral amines. Hydroamination via metal-catalyzed hydrogen atom transfer (HAT) with good regioselectivity functional group tolerance has been reported, however, high enantioselectivity not achieved due the lack suitable ligands. Here we report ligand-promoted cobalt-catalyzed Markovnikov-type selective radical diazo compounds. This operationally simple protocol uses unsymmetric NNN-tridentate (UNT) ligand, readily available hydrosilanes construct hydrazones tolerance. The can undergo nitrogen-nitrogen bond cleavage smoothly deliver amine derivatives. Additionally, asymmetric unactivated aliphatic terminal using N-imidazolinylphenyl 8-aminoquinoline (IPAQ) ligands also afford derivatives enantioselectivities.

Language: Английский

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Cobalt‐Catalyzed Asymmetric Hydrogenation of C=N Bonds Enabled by Assisted Coordination and Nonbonding Interactions

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(44), P. 15767 - 15771

Published: Aug. 29, 2019

An efficient cobalt-catalyzed asymmetric hydrogenation of C=N bonds has been realized. Chiral hydrazines were obtained in high yields and with excellent enantioselectivities (95-98 % ee). The went smoothly at up to 2000 substrate/catalyst on a gram scale. success this reaction relies the presence an NHBz group substrates, reactivity enantioselectivity improved by assisted coordination cobalt atom nonbonding interaction ligand. Furthermore, practical applications for synthesis several useful chiral nitrogen-containing compounds.

Language: Английский

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Nickel-Catalyzed Multicomponent Coupling: Synthesis of α-Chiral Ketones by Reductive Hydrocarbonylation of Alkenes

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(35), P. 14089 - 14096

Published: Aug. 26, 2021

A nickel-catalyzed, multicomponent regio- and enantioselective coupling via sequential hydroformylation carbonylation from readily available starting materials has been developed. This modular hydrofunctionalization strategy enables the straightforward reductive hydrocarbonylation of a broad range unactivated alkenes to produce wide variety unsymmetrical dialkyl ketones bearing functionalized α-stereocenter, including enantioenriched chiral α-aryl α-amino ketones. It uses bisoxazoline as ligand, silane reductant, chloroformate safe CO source, racemic secondary benzyl chloride or an N-hydroxyphthalimide (NHP) ester protected acid alkylation reagent. The benign nature this process renders method suitable for late-stage functionalization complex molecules.

Language: Английский

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