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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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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Ligand-Enabled Cu-Catalyzed Stereoselective Synthesis of P-Stereogenic ProTides

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(45), С. 31339 - 31347

Опубликована: Ноя. 4, 2024

Nucleoside analogues have seen significant advancements in treating viral infections and cancer through ProTide technology, leading to a series of FDA-approved drugs such as sofosbuvir, tenofovir alafenamide, remdesivir. The stereochemical configuration at the phosphorus center ProTides significantly influences their pharmacological properties, necessitating efficient stereoselective synthesis. Traditional methods using chiral auxiliaries or nonracemic phosphorylating agents are labor-intensive inefficient, while recent organocatalytic approaches, despite promise, still face limitations. Herein, we present novel approach employing metal complexes for assembly P-stereogenic via asymmetric P-O bond formation. This leverages catalyst activate electrophilic reagent, facilitating base-promoted nucleophilic replacement pathway. Our protocol, featuring mild reaction conditions broad applicability, enables highly synthesis previously inaccessible (

Язык: Английский

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The Effect of Basic Ligands and Alkenes on the Regioselectivity of C−H Additions of Tertiary Amines to Alkenes

Chemistry - A European Journal, Год журнала: 2024, Номер 30(32)

Опубликована: Апрель 4, 2024

Abstract Highly regioselective C−H alkylation reactions of tertiary anilines and alkyl amines with simple alkenes have been achieved by the use imidazolin‐2‐iminato scandium complexes. This protocol provided an efficient atom‐economical route to structurally diverse amine derivatives. The basic ligand, a coordinating THF in catalyst substitution alkene substrates were found switch regioselectivity presumably due generation different types catalytically active species or formation relatively stable intermediates. On basis deuterium labeling experiments KIE experiments, possible catalytical cycles understand reaction mechanism as well regioselectivity.

Язык: Английский

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Chemo-, regio- and enantioselective hydroformylation of trisubstituted cyclopropenes: access to chiral quaternary cyclopropanes

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

Опубликована: Июль 29, 2024

Catalytic asymmetric synthesis of polysubstituted chiral cyclopropane presents a significant challenge in organic due to the difficulty enantioselective control. Here we report rhodium-catalyzed highly chemo-, regio- and hydroformylation trisubstituted cyclopropenes affording quaternary cyclopropanes. Importantly, easy made sterically bulky ligand L1 can effectively suppress hydrogenation decomposition reactions give cyclopropanes with high enantioselectivities for both aryl alkyl functionalized substrates. Control experiments computational studies reveal hindered well-defined pocket instead substrates bearing electron-withdrawing diester groups is important controlling enantioselectivity regioselectivity. Scale-up reaction follow-up diverse transformations are also presented. Density Functional theory (DFT) computations suggest that enantio-selectivities originate from cyclopropene insertion Rh-H bond. The regioselectivity found benefit presence more efficient noncovalent interactions (NCIs) manifesting form C–H···Cl, C–H···N, l.p(Cl)···π contacts. Transition-metal-catalyzed represents an atom-economic clean approach preparation aldehydes efficiency. Herein, authors

Язык: Английский

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Recent advances in hydrofunctionalisation of cyclopropenes via carbon–heteroatom bond formation

Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review highlights recent advances in the hydrofunctionalisation of cyclopropenes through formation carbon–heteroatom bonds for synthesis polysubstituted cyclopropanes.

Язык: Английский

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Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis

Angewandte Chemie, Год журнала: 2024, Номер 137(1)

Опубликована: Сен. 10, 2024

Abstract Different from the reported work focusing on construction of single P ‐ or C ‐stereocenter via hydrophosphinylation unsaturated carbon bonds, highly diastereo‐ and enantioselective reaction allenes, conjugated enynes 1,3‐dienes is achieved a designed Pd/Co dual catalysis newly modified masked phosphinylating reagent. A series allyl motifs bearing both tertiary are prepared in generally good yields, >20 : 1 dr, rr 99 % ee. The unprecedented 1,3‐enynes established to generate skeletons containing nonadjacent chiral axis. first stereodivergent also developed achieve all four ‐containing stereoisomers. present protocol features use only 3‐minutes time 0.1 catalyst, with observation up 730 TON. set mechanistic studies reveal necessity roles two metal catalysts corroborate synergistic process.

Язык: Английский

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Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(1)

Опубликована: Сен. 10, 2024

Different from the reported work focusing on construction of single P- or C-stereocenter via hydrophosphinylation unsaturated carbon bonds, highly diastereo- and enantioselective reaction allenes, conjugated enynes 1,3-dienes is achieved a designed Pd/Co dual catalysis newly modified masked phosphinylating reagent. A series allyl motifs bearing both tertiary C- P-stereocenter are prepared in generally good yields, >20 : 1 dr, rr 99 % ee. The unprecedented 1,3-enynes established to generate skeletons containing nonadjacent chiral axis. first stereodivergent also developed achieve all four P-containing stereoisomers. present protocol features use only 3-minutes time 0.1 catalyst, with observation up 730 TON. set mechanistic studies reveal necessity roles two metal catalysts corroborate synergistic process.

Язык: Английский

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Cobalt-Catalyzed Stereoselective Synthesis of Chiral Gem-Difluorocyclopropanes with Vicinal Stereocenters

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(23), С. 6617 - 6626

Опубликована: Янв. 1, 2024

We present a cobalt-catalyzed regio-, diastereo-, and enantioselective hydroalkylation of gem -difluorocyclopropenes, accessing chiral -difluorocyclopropanes with vicinal stereocenters.

Язык: Английский

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Advances in Catalytic Asymmetric Hydrogen-Phosphine/Phosphorus Functionalization of Unsaturated Carbon-Carbon Bonds

Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(12), С. 3647 - 3647

Опубликована: Янв. 1, 2024

Язык: Английский

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