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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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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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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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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Co(III)-Catalyzed, N-Amino-Directed C–H Coupling with 4-Hydroxy-2-alkynoates for Indole Synthesis

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

Conventional synthetic organic chemistry typically relies on site-centered reactivity for the reaction discovery. Herein, skeleton-chaperoned is exploited development, with skeleton utilized as a structural scaffold assisting functional group activation into proper sequence. A Co(III) catalytic method has been developed N-amino-directed C-H coupling 4-hydroxy-2-alkynoates, allowing convenient access to 2-alkene-3-carboxylic acid type indole derivatives. This features phenyl/pyrrole/lactone skeleton-chaperone and simultaneous conversion of five groups.

Language: Английский

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Catalyst-controlled regiodivergence and stereodivergence in formal cross-[4+2] cycloadditions: The unique effect of bismuth(III)

Science Advances, Journal Year: 2025, Volume and Issue: 11(13)

Published: March 26, 2025

The [4+2] cycloaddition is crucial for constructing six-membered rings in pharmaceuticals and natural products. Cross-[4+2] cycloadditions offer greater product diversity than traditional diene-dienophile reactions due to multiple possible pathways. However, precise control over regio- stereoselectivity various isomers remains a great challenge. This study reports catalyst-controlled regiodivergent formal cross-cycloadditions of acyclic dienes enones, significantly enhancing access diverse pyrazole-fused spirooxindoles. Chiral phosphoric acid (CPA) catalysis enables endoselective cycloadditions, while Bi(III) with CPA ligand yields [2+4] products high stereoselectivity. A Claisen rearrangement the adduct produces exo-selective product, further increasing stereochemical enabling synthesis six stereo-isomers from single substrate set. DFT calculations reveal that reverses regioselectivity by repositioning reactants pocket stabilizing enone oxygen’s negative charge. In addition, 3as demonstrates therapeutic potential against triple-negative breast cancer, an IC 50 8.5 μM MDA-MB-453 cells.

Language: Английский

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Cobalt-Catalyzed Diester Formation with CO at Atmospheric Pressure via Three-Component Reactions

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 28, 2025

We propose a cobalt-catalyzed three-component reaction conducted under mild conditions. Following the carbonyl insertion at atmospheric pressure, proceeds via nucleophilic attack by alcohols to form diesters. Notably, scope of reagents can be extended include range anilines. Furthermore, products this transformation serve as crucial synthetic building blocks for diverse organic synthesis processes, with subsequent derivatizations yielding promising results.

Language: Английский

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Copper-catalyzed oxidative sulfenylation and alkylation of indolin-2-ones for direct construction of sulfur-substituted quaternary carbons

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(11), P. 3131 - 3136

Published: Jan. 1, 2024

A rapid and green one-pot access to S -substituted quaternary carbon centers from commercially available feedstock chemicals has been established, providing complex molecules with high chemoselectivity by the use of air as terminal oxidant.

Language: Английский

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Divergent Reactions of α-Diazo 1,3-Dicarbonyl Compounds with Allylic Carbonates Involving Ketene versus Carbene Intermediates Enabled by Cooperative Rh(II)/Pd(0) Dual Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(37), P. 7920 - 7925

Published: Sept. 9, 2024

A cooperative Rh(II)/Pd(0) dual-catalysis strategy that enabled divergent reactions of α-diazo 1,3-dicarbonyl compounds with allylic carbonates involving ketene versus carbene intermediates is described. The efficient synthesis α-quaternary allylated β-keto-esters was accomplished by the alkylation compounds. Alternatively, an unprecedented (1+4) annulation 2-(hydroxymethyl)allyl via dual catalysis also successfully developed, affording a wide variety tetrahydrofurans in good to high yields.

Language: Английский

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Three‐component allylic alkylation reaction of α‐diazo ketones with water and allyl carbonates for construction of homoallylic alcohols

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(17), P. 3616 - 3623

Published: June 20, 2024

Abstract A three‐component allylic alkylation reaction of α‐diazo ketones, water and allyl carbonate under the cooperative catalysis Rh 2 (OAc) 4 , Pd (dba) 3 Brønsted acid was disclosed. This method provides an expeditious access to α‐keto homoallylic alcohols in good high yields. Controlled experiments support that transformations proceed through cross‐interception two active intermediates Pd‐allyl species enol derived from oxonium ylides. Moreover, synthetic generated products enable creation motifs enriched with dense functional groups, underscoring their potential as valuable building blocks.

Language: Английский

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