Asymmetric transformations enabled by synergistic dual transition-metal catalysis

Chem Catalysis, Год журнала: 2022, Номер 3(1), С. 100455 - 100455

Опубликована: Ноя. 17, 2022

Язык: Английский

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Divergent Geminal Alkynylation–Allylation and Acylation–Allylation of Carbenes: Evolution and Roles of Two Transition-Metal Catalysts

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4727 - 4740

Опубликована: Фев. 8, 2024

Cooperative bimetallic catalysis to access novel reactivities is a powerful strategy for reaction development in transition-metal-catalyzed chemistry. Particularly, elucidation of the evolution two transition-metal catalysts and understanding their roles dual are among most fundamental goals catalysis. Herein, three-component terminal alkyne, diazo ester, an allylic carbonate was successfully developed via cooperative Cu/Rh with Xantphos as ligand, providing highly efficient 1,5-enynes all-carbon quaternary center that can be used immediate synthetic precursors complex cyclic molecules. Notably, Meyer–Schuster rearrangement involved reactions using propargylic alcohols, resulting unprecedented acylation–allylation carbenes. Mechanistic studies suggested course Cu(I) species might aggregate some types Cu clusters nanoparticles (NPs), while Rh(II)2 precursor dissociate mono-Rh species, wherein NPs proposed responsible alkynylation carbenes work cooperation Xantphos-coordinated dirhodium(II) or Rh(I)-catalyzed alkylation.

Язык: Английский

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Dirhodium–Palladium Dual-Catalyzed [1 + 1 + 3] Annulation to Heterocycles Using Primary Amines or H₂O as the Heteroatom Sources

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 7, 2025

The ever-increasing demand in chemical biology and medicinal research requires the development of new synthetic methods for rapid construction libraries heterocycles from simple raw materials. In this context, utilization primary amines or H2O as N- O-sources assembly a heterocyclic ring skeleton is highly desirable viewpoint atom- step-economy. Herein, we describe efficient three-component reaction diazo, allylic diacetates, commercially available anilines (or H2O) to access structurally diverse pyrrolidine tetrahydrofuran derivatives. This formal [1 + 1 3] annulation features high efficiency, good yields, broad functional group compatibility, making it versatile robust platform (formal) synthesis several important bioactive molecules. Mechanistic studies suggested that dirhodium–palladium bimetallic relay catalysis should play key role successive steps current reaction, including sequential carbene insertion into X–H bond double substitutions, thus allowing building up molecular complexity these

Язык: Английский

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Overcoming O–H Insertion to Para-Selective C–H Functionalization of Free Phenols: Rh(II)/Xantphos Catalyzed Geminal Difunctionalization of Diazo Compounds

ACS Central Science, Год журнала: 2022, Номер 8(5), С. 581 - 589

Опубликована: Апрель 20, 2022

Para-selective C-H functionalization of free phenols by metal carbenoids is rather challenging due to the generally more favorable competing O-H insertion. Herein, with use combination Rh(II) and a Xantphos ligand as catalyst, novel multicomponent reaction phenols, diazoesters, allylic carbonates was successfully developed, affording wide variety phenol derivatives, bearing an all-carbon quaternary center synthetically useful unit. This likely occur through tandem process carbene-induced para-selective functionalization, followed Rh(II)/Xantphos-catalyzed allylation. The distinctive reactivity than insertion for carbenoid intermediate, combined features excellent functional group compatibility, high atom step economy, ease in further diversification products, might render this protocol highly attractive facile unprotected phenols.

Язык: Английский

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Diastereo‐ and Enantioselective Synthesis of Bisbenzannulated Spiroketals and Spiroaminals by Ir/Ag/Acid Ternary Catalysis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(42)

Опубликована: Авг. 4, 2022

Abstract We reported herein an iridium/silver/acid ternary catalytic system to access bisbenzannulated [6,6]‐spiroketals in high efficiency with generally diastereo‐ and enantioselectivities (up >20 : 1 dr, >99 % ee). In this procedure, readily available o ‐alkynylacetophenones undergo cycloisomerization generate isochromenes situ that participate stereoselective allylation/spiroketalization sequence 2‐(1‐hydroxyallyl)phenols. Meanwhile, 2‐(1‐hydroxyallyl)anilines were also compatible cascade reaction, furnishing structurally novel [6,6]‐spiroaminals good diastereoselectivities (8 1–12 dr) excellent (98 %–>99 Moreover, experimental studies theoretical calculations performed illustrate the reaction mechanism stereochemistry.

Язык: Английский

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Asymmetric Three-Component Reaction of Enynal with Alcohol and Imine as An Expeditious Track to Afford Chiral α-Furyl-β-amino Carboxylate Derivatives

ACS Catalysis, Год журнала: 2022, Номер 12(22), С. 14185 - 14193

Опубликована: Ноя. 4, 2022

Herein, we report an achiral dirhodium complex and chiral phosphoric acid cooperatively catalyzed asymmetric three-component reaction of enynal with alcohol imine, affording α-furyl-β-amino carboxylates in good to high yields generally excellent stereoselectivity. The successful introduction as a carbene precursor this provides expeditious track prepare furan derivatives adjacent quaternary tertiary stereocenters. starting materials are stable readily available, the method features 100% atom economy bond-formation efficiency. This is highly enantioselective gem-difunctionalization metal generated situ from enynal. These products could be smoothly converted polycyclic frameworks drug-conjugated through different cycloaddition reactions.

Язык: Английский

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Synergistic catalysis for stereocontrol of prochiral nucleophiles in palladium-catalyzed asymmetric allylic substitution

Science China Chemistry, Год журнала: 2023, Номер 66(8), С. 2238 - 2255

Опубликована: Июль 20, 2023

Язык: Английский

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Chiral organophosphates as ligands in asymmetric metal catalysis

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(12), С. 3080 - 3109

Опубликована: Янв. 1, 2023

Chiral phosphates have successfully been used as ligands in asymmetric metal-catalysis. This Minireview discusses the most recent examples, including main-group catalysis, transition-metal catalysis and by rare-earth metals.

Язык: Английский

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Enantioselective Synthesis of Biscyclopropanes Using Alkynes as Dicarbene Equivalents

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(29)

Опубликована: Май 22, 2023

Chiral biscyclopropanes are an important skeleton in many bioactive molecules. However, there few routes to synthesize these molecules with high stereoselectivity due the nature of multiple stereocenters. Herein, we report first example Rh2 (II)-catalyzed enantioselective synthesis bicyclopropanes alkynes as dicarbene equivalents. The 4-5 vicinal stereocenters and 2-3 all-carbon quaternary centers were constructed excellent stereoselectivity. This protocol features efficiency functional group tolerance. Moreover, was also extended cascaded cyclopropanation/cyclopropenation stereoselectivities. In processes, both sp-carbons alkyne converted into stereogenic sp3 -carbons. Experimental density theory (DFT) calculations revealed that cooperative weak hydrogen bonds between substrates dirhodium catalyst may play key roles this reaction.

Язык: Английский

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Overview of Transition Metal Catalyzed Multicomponent Reactions Based on Trapping of Allylic Electrophiles

ChemCatChem, Год журнала: 2024, Номер 16(4)

Опубликована: Янв. 11, 2024

Abstract Multicomponent reactions provide an excellent approach toward quaternary carbon centres utilizing convergent chemical in a highly selective manner under one‐pot conditions. The reactivity of substrates and metal catalysts is carefully controlled, precluding the formation side‐products. In this context, transition catalyzed onium ylides generated via diazo precursors nucleophiles with third component (an electrophile) have garnered significant attention. Using allylic precursor as electrophilic partner provides opportunities to construct all‐carbon centres. Furthermore, presence allyl fragment multicomponent product serves pivotal handle for carrying out subsequent modifications. Several recent studies employed Rh, Pd, dual Rh/Pd catalytic systems involving alkylation that proceed synergistic or relay pathway. Although not significantly successful, few cases, asymmetric induction achieved through chiral phosphoric acids phosphine ligands. Limited substrate catalyst scope underlying mechanistic complexities posed formidable challenges, slowing advancement reactions. This review details using readily available like compounds, carbonates, (R‐OH, R‐NH 2 , etc .) forming complex organic compounds. Our primary objective discuss issues may facilitate progress field.

Язык: Английский

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