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

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(7), P. 4727 - 4740

Published: Feb. 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.

Language: 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, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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

Language: Английский

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

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(4)

Published: Jan. 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.

Language: Английский

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Cooperative Bimetallic Catalysis via One‐Metal/Two‐Ligands: Mechanistic Insights of Polyfluoroarylation‐Allylation of Diazo Compounds

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: June 16, 2023

Metal/ligand in situ assembly is crucial for tailoring the reactivity & selectivity transition metal catalysis. Cooperative catalysis via a single metal/two ligands still underdeveloped, since it rather challenging to harness distinct profiles of species generated by self-assembly precursor with mixture different ligands. Herein, we report catalytic system composed three-component reaction polyfluoroarene, α-diazo ester, and allylic electrophile, leading highly efficient construction densely functionalized quaternary carbon centers, that are otherwise hardly accessible. Mechanistic studies suggest this follows cooperative bimetallic pathway two catalysts profiles, which assembled from work concert escort transformation.

Language: Английский

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Axial Ligand Enables Synthesis of Allenylsilane through Dirhodium(II) Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: June 18, 2024

Described herein is a dirhodium(II)-catalyzed silylation of propargyl esters with hydrosilanes, using tertiary amines as axial ligands. By adopting this strategy, range versatile and useful allenylsilanes can be achieved good yields. This reaction not only represents S

Language: Английский

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Rh(II)/Pd(0) Dual-Catalyzed Regio-Divergent Three-Component Propargylic Substitution

JACS Au, Journal Year: 2023, Volume and Issue: 3(10), P. 2862 - 2872

Published: Sept. 25, 2023

Regio-divergent propargylic substitution to generate functionally diverse products from identical starting materials remains a formidable challenge, probably due the unpredictable regiochemical complexity. In practically, synthesis of α-quaternary propargylic-substituted is still much less developed, and preprepared nucleophiles are generally applied in this type reaction with substrates, which limits efficiency diversity obtained products. Herein, we disclose unprecedented three-component α-diazo esters amines carbonates under dirhodium/palladium dual catalysis. The key success multicomponent avoid two-component side reactions through tandem process dirhodium(II)-catalyzed carbene insertion palladium-catalyzed regiodivergent substitution. judicious selection diphosphine (dppf) or monophosphine (tBuBrettphos) as ligand crucial for different switchable way, 1,3-dienyl propargylated products, high regio- chemoselectivities.

Language: Английский

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Mechanism and stereoselectivity in metal and enzyme catalyzed carbene insertion into X–H and C(sp²)–H bonds

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(22), P. 11004 - 11044

Published: Jan. 1, 2024

This review provides a mechanistic overview of asymmetric Fe, Cu, Pd, Rh, Au and heme-based enzymes catalyzed carbene insertion reactions to construct C–X (X = O, N, S, etc. ) C–C bonds, focusing on the stereochemical models.

Language: Английский

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Selective Construction of All-Carbon Quaternary Centers via Relay Catalysis of Indole C–H Functionalization/Allylic Alkylation

Organic Letters, Journal Year: 2022, Volume and Issue: 24(45), P. 8423 - 8428

Published: Nov. 4, 2022

Herein, a novel [Rh]2-catalyzed three-component reaction of readily accessible indoles, diazo compounds, and allylic compounds is developed via relay carbene-induced C-H functionalization alkylation process, affording diverse C3-substituted indoles bearing all-carbon quaternary centers in good yields with high atom step economy. Moreover, enantioselective control achieved using (-)-DIOP type ligand, thus providing an efficient method for constructing enantioenriched indole derivatives stereocenter.

Language: Английский

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Enantioselective Alkylation of Primary C(sp³)–H Bonds in N-Methyl Tertiary Amine Enabled by Iridium Complex of Axially Chiral β-Aryl Porphyrins

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

A fine-tuning of enantioselective carbene insertion into primary C(

Language: Английский

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Enantioselective β-alkenylation of α,β-unsaturated aldehydes via chiral biphosphine ligand modified dirhodium(II) catalysis

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Language: Английский

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