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

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(38)

Опубликована: Июнь 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

Язык: Английский

---

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

---

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

Chemical Society Reviews, Год журнала: 2024, Номер 53(22), С. 11004 - 11044

Опубликована: Янв. 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.

Язык: Английский

---

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

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

Язык: Английский

---

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

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 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.

Язык: Английский

---

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

Science Advances, Год журнала: 2025, Номер 11(13)

Опубликована: Март 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.

Язык: Английский

---

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

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 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.

Язык: Английский

---

Visible‐Light‐Driven Multicomponent Reactions of Diazosulfonium Triflates with Amines and CS₂ or CO₂: Direct Synthesis of Bis‐Dithiocarbamates/Carbamates

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 19, 2025

Comprehensive Summary Visible light‐induced transformation of CO 2 and CS into value‐added products has attracted worldwide attention because it mimics nature. In this context, although visible‐light‐induced direct synthesis dithiocarbamates carbamates employing SO as a C1 source been reported, all these reactions are limited to the preparation S ‐alkyl mono‐dithiocarbamates O mono‐carbamates. Herein, we report visible‐light photoredox‐catalyzed multicomponent reaction diazosulfonium triflates with amines or . Mechanistic studies indicate that diazomethyl radicals might be generated key intermediates, thus providing direction for application other radical acceptors.

Язык: Английский

---

Efficient Allylation of Dihalides: A Versatile Approach to C/N/O‐Functionalized Derivatives

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 19, 2025

Comprehensive Summary This study presents an efficient and innovative allylation strategy utilizing C/N/O nucleophilic reagents with attenuated reactivity, enabling the construction of versatile allyl compounds. The approach focuses on sequential dihalides in large‐scale chemical manufacturing, effectively addressing challenge achieving selectivity cascade reactions. methodology is centered Cu‐catalyzed C ‐olefination alkynes dihalides, significantly expediting synthesis a diverse array finely conjugated enyne derivatives. Furthermore, base‐facilitated condensation process has been developed to achieve N ‐allylation hydrazines, yielding wide range trisubstituted alkenyl hydrazones. Additionally, protocol enables high‐value ester compounds through O or esterification dihalides. transformation also facilitates one‐step variety essential pharmaceuticals, demonstrating its broad synthetic utility potential.

Язык: Английский

---

Catalyst-Controlled Divergent Synthesis of Bicyclo[2.1.1]hexanes and Cyclobutenes: The Unique Effect of Au(I)

JACS Au, Год журнала: 2025, Номер unknown

Опубликована: Май 22, 2025

Язык: Английский

---