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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3405 - 3415

Опубликована: Янв. 29, 2024

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

Язык: Английский

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Catalytic desymmetrization reactions to synthesize all-carbon quaternary stereocentres

Nature Synthesis, Год журнала: 2023, Номер 2(11), С. 1020 - 1036

Опубликована: Окт. 16, 2023

Язык: Английский

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Cobalt‐Catalyzed Facial‐Selective Hydroalkylation of Cyclopropenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 31, 2023

Abstract Cyclopropene hydrofunctionalization has been a promising strategy for accessing multi‐substituted cyclopropanes; however, cyclopropene hydroalkylation remains underdeveloped. Herein, we report low‐valent CoH‐catalyzed facial‐selective to access cyclopropanes. This reaction exhibits broad substrate scope of alkyl halides and cyclopropenes tolerates many functional groups. Moderate‐to‐good facial‐selectivity is obtained without any directing Mechanism studies provide evidence that radicals are generated from irreversible CoH insertion responsible the facial‐selectivity. Our preliminary exploration demonstrates asymmetric can be realized conspicuous auxiliary

Язык: Английский

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Copper‐Phosphido Catalysis: Enantioselective Addition of Phosphines to Cyclopropenes**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)

Опубликована: Июнь 19, 2023

We describe a copper catalyst that promotes the addition of phosphines to cyclopropenes at ambient temperature. A range cyclopropylphosphines bearing different steric and electronic properties can now be accessed in high yields enantioselectivities. Enrichment phosphorus stereocenters is also demonstrated via Dynamic Kinetic Asymmetric Transformation (DyKAT) process. combined experimental theoretical mechanistic study supports an elementary step featuring insertion Cu

Язык: Английский

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Copper(I)‐Catalyzed Asymmetric Hydrophosphination of 3,3‐Disubstituted Cyclopropenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)

Опубликована: Авг. 18, 2023

Herein, a copper(I)-catalyzed asymmetric hydrophosphination of 3,3-disubstituted cyclopropenes is reported. It provides series phosphine derivatives in high to excellent diastereo- and enantioselectivities. The methodology enjoys broad substrate scope on both diarylphosphines. stereoselectivity attributed the stability Cu(I)-(R,R)-QUINOXP* complex presence stoichiometric HPPh2 produced phosphines, high-performance induction complex. Finally, method used for synthesis new chiral phosphine-olefin compounds built cyclopropane skeleton, one which serves as wonderful ligand Rh-catalyzed conjugate addition phenylboronic acid various α,β-unsaturated compounds.

Язык: Английский

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Desymmetrization–Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 18892 - 18898

Опубликована: Июль 5, 2024

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated synthesis series chiral functionalized cyclopropanes with high yield, enantioselectivity, diastereoselectivity (44 examples, up 93% yield >99% ee). A possible mechanism involving cyclopropene desymmetrization Co-H species imine addition Co-alkyl was proposed. study provides novel route important extends frontier metallaphotoredox

Язык: Английский

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Enantioselective synthesis of chiral α,α-dialkyl indoles and related azoles by cobalt-catalyzed hydroalkylation and regioselectivity switch

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 6, 2024

Abstract General, catalytic and enantioselective construction of chiral α,α -dialkyl indoles represents an important yet challenging objective to be developed. Herein we describe a cobalt catalyzed anti- Markovnikov alkene hydroalkylation via the remote stereocontrol for synthesis other N -heterocycles. This asymmetric C(sp 3 )−C(sp ) coupling features high flexibility in introducing diverse set alkyl groups at α -position The utility this methodology has been demonstrated by late-stage functionalization drug molecules, bioactive natural products functional materials, identification class molecules exhibiting anti-apoptosis activities UVB-irradiated HaCaT cells. Ligands play vital role controlling reaction regioselectivity. Changing ligand from bi-dentate L6 tridentate L12 enables CoH-catalyzed hydroalkylation. Mechanistic studies disclose that involves migratory insertion process while MHAT process.

Язык: Английский

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Copper-Catalyzed Hydroamination: Enantioselective Addition of Pyrazoles to Cyclopropenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(27), С. 14573 - 14580

Опубликована: Июнь 30, 2023

Chiral N-cyclopropyl pyrazoles and structurally related heterocycles are prepared using an earth-abundant copper catalyst under mild reaction conditions with high regio-, diastereo-, enantiocontrol. The observed N2:N1 regioselectivity favors the more hindered nitrogen of pyrazole. Experimental DFT studies support a unique mechanism that features five-centered aminocupration.

Язык: Английский

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NiH-Catalyzed Regio- and Enantioselective Hydroalkylation for the Synthesis of β- or γ-Branched Chiral Aromatic N-Heterocycles

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(40), С. 22122 - 22134

Опубликована: Сен. 25, 2023

A nickel hydride-catalyzed regio- and enantioselective hydroalkylation reaction was developed to give access a library of chiral β- or γ-branched aromatic N-heterocycles. This intriguing asymmetric transformation features excellent selectivities, step- atom-economies, generating two kinds products through one synthetic strategy. Furthermore, the possible mechanism extensively investigated using numerous control experiments density functional theory calculations.

Язык: Английский

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Construction of Acyclic All‐Carbon Quaternary Stereocenters and 1,3‐Nonadjacent Stereoelements via Organo/Metal Dual Catalyzed Asymmetric Allenylic Substitution of Aldehydes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(20)

Опубликована: Март 13, 2023

A method for the asymmetric construction of functionalized acyclic all-carbon quaternary stereocenters and 1,3-nonadjacent stereoelements has been developed via organo/metal dual catalyzed allenylic substitution branched linear aldehydes, by developing an unknown secondary-secondary diamine as enabling organocatalyst. Although it is believed that diamines are difficult to be used organocatalysts in catalysis, this study demonstrates such can successfully combined with a metal catalyst catalysis. Our enables two important classes motifs which were previously access, axially chiral allene-containing bearing allenyl axial chirality central chirality, good yields high enantio- diastereoselectivity.

Язык: Английский

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