Copper-Catalyzed One-Step Formation of Four C–N Bonds toward Polyfunctionalized Triazoles via Multicomponent Reaction DOI

Xuelun Duan,

Nan Zheng,

Gongbo Liu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(32), P. 6006 - 6012

Published: Aug. 5, 2022

A novel four-component reaction of alkynes, amines, azides, and 2H-azirines has been developed for the first time by efficient formation four C–N bonds in one step under mild conditions, rapidly preparing polyfunctionalized triazoles with molecular diversity involving three different intermediates copper–acetylide, copper–allenylidene, copper–vinyl nitrene. Propargylic ester is disclosed as a "three-in-one" building block possessing triplicate cycloaddition nucleophilic electrophilic properties, which could enable such transformation high yields, broad substrate scope, functionalization.

Language: Английский

Visible Light-Induced Reactions of Diazo Compounds and Their Precursors DOI
Ziyan Zhang, Vladimir Gevorgyan

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(11), P. 7214 - 7261

Published: May 16, 2024

In recent years, visible light-induced reactions of diazo compounds have attracted increasing attention in organic synthesis, leading to improvement existing reactions, as well the discovery unprecedented transformations. Thus, photochemical or photocatalytic generation both carbenes and radicals provide milder tools toward these key intermediates for many valuable However, vast majority transformations represent new reactivity modes compounds, which are achieved by decomposition photoredox catalysis. particular, use a redox-active photocatalysts opens avenue plethora radical reactions. The application methods led inaccessible classical associated with metal carbenes. most cases, act sources but can also serve acceptors. Importantly, described processes operate under mild, practical conditions. This Review describes this subfield compound chemistry, particularly focusing on advancements.

Language: Английский

Citations

56
Ring expansion of indene by photoredox-enabled functionalized carbon-atom insertion DOI
Fu‐Peng Wu, Chetan C. Chintawar, Rémy F. Lalisse

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(3), P. 242 - 251

Published: Jan. 9, 2024

Language: Английский

Citations

37
Generation of Stereocenters via Single-Carbon-Atom Doping Using N-Isocyanides DOI
Hayato Fujimoto,

Teruki Nishioka,

Kazuya Imachi

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

Atomic carbon remains a challenging species for organic synthesis despite its potential to form four covalent bonds in single step. Single-carbon-atom doping (SCAD) offers powerful approach enhancing molecular complexity one process without atom loss. However, synthetically viable SCAD reactions capable of generating stereocenters have not been realized. Here, we report an reaction that creates by unlocking the reactivity (N-isocyanoimino)phosphorane as atomic equivalent. This reagent facilitates single-step conversion various acyl chlorides into homologated α-chloro cyclic ketones, proceeding via formation different bonds: C-Cl, C-H, and two C-C at incorporated atom.

Language: Английский

Citations

2
Diazo compounds: Recent applications in synthetic organic chemistry and beyond DOI
Jianbo Wang

Tetrahedron Letters, Journal Year: 2022, Volume and Issue: 108, P. 154135 - 154135

Published: Sept. 12, 2022

Language: Английский

Citations

41
Generating Fischer-Type Rh-Carbenes with Rh-Carbynoids DOI Creative Commons

Eric Palomo,

Akhilesh K. Sharma, Zhaofeng Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 4975 - 4981

Published: Feb. 22, 2023

We describe the first catalytic generation of Fischer-type acyloxy Rh(II)-carbenes from carboxylic acids and Rh(II)-carbynoids. This novel class transient donor/acceptor evolved through a cyclopropanation process providing access to densely functionalized cyclopropyl-fused lactones with excellent diastereoselectivity. DFT calculations allowed analysis properties Rh(II)-carbynoids as well characterization mechanism.

Language: Английский

Citations

29
Enantioselective Multifunctionalization with Rh Carbynoids DOI
Yu Qian,

Jie Tang,

Xiaoyu Zhou

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(48), P. 26403 - 26411

Published: Nov. 22, 2023

Multifunctionalization from the interception of active intermediates is an attractive synthetic strategy for efficient construction complex molecular scaffolds in atom and step economic fashion. However, design reactions involving metal carbynoids that exhibit carbene/carbocation behavior currently limited, developing catalyst-controlled highly enantioselective versions poses significant challenges. In this study, we present first asymmetric trifunctionalization with rhodium carbynoids. This reaction unveils distinctive reactivity carbynoid precursor, enabling it to react simultaneously two nucleophiles one electrophile. process involves formation distinct carbene ylides alcohol/carbamate trapping ylide imine, resulting three new bonds. Furthermore, allows divergent synthesis a wide array β-amino esters high yields exceptional enantioselectivity.

Language: Английский

Citations

24
Reactivity of α-diazo sulfonium salts: rhodium-catalysed ring expansion of indenes to naphthalenes DOI Creative Commons

Sven Timmann,

Tun-Hui Wu,

Christopher Golz

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(16), P. 5938 - 5943

Published: Jan. 1, 2024

Cyclopropyl-substituted sulfonium salts are obtained by Rh-catalysed addition of α-diazo dibenzothiophenium to olefins. When indenes used as substrates, initially formed cyclopropyl rings open with concomitant elimination dibenzothiophene, enabling access 2-substituted naphthalenes.

Language: Английский

Citations

11
Trifluoromethyl Rhodium‐Carbynoid in [2+1+2] Cycloadditions DOI
Wenwen Zhao,

Meng‐Yang Tian,

Yilin Zhou

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Jan. 18, 2024

Abstract Trifluoromethyl cationic carbyne (CF 3 C + :) possessing dual carbene‐carbocation behavior emulated as trifluoromethyl metal‐carbynoid =M) has not been explored yet, and its reaction characteristics are unknown. Herein, a novel α‐diazotrifluoroethyl sulfonium salt was prepared used in Rh‐catalyzed three‐component [2+1+2] cycloadditions for the first time with commercially available N ‐fused heteroarenes nitriles, yielding series of imidazo[1,5‐ ] ‐heterocycles that interest medicinal chemistry, which insertion Rh‐carbynoid =Rh) into C=N bonds involved. This strategy demonstrates synthetic applications late‐stage modification pharmaceuticals, construction CD ‐containing ‐heterocycles, gram‐scale experiments, synthesis phosphodiesterase 10A inhibitor analog. These highly valuable modifiable exhibit good antitumor activity vitro, thus demonstrating their potential chemistry.

Language: Английский

Citations

9
Mechanical‐Force‐Induced Non‐spontaneous Dehalogenative Deuteration of Aromatic Iodides Enabled by Using Piezoelectric Materials as a Redox Catalyst DOI

Ruiling Qu,

Shan Wan, Xuemei Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)

Published: April 30, 2024

Abstract The development of green and efficient deuteration methods is great significance for various fields such as organic synthesis, analytical chemistry, medicinal chemistry. Herein, we have developed a dehalogenative strategy using piezoelectric materials catalysts in solid‐phase system under ball‐milling conditions. This non‐spontaneous reaction induced by mechanical force. D 2 O can serve both deuterium source an electron donor the transformation, eliminating need additional stoichiometric exogenous reductants. A series (hetero)aryl iodides be transformed into deuterated products with high incorporation. method not only effectively overcomes existing synthetic challenges but also used labelling drug molecules derivatives. Bioactivity experiments molecule suggest that D‐ipriflavone enhances inhibitory effects on osteoclast differentiation BMDMs vitro .

Language: Английский

Citations

8
Catalytic Synthesis of Cyclopropenium Cations with Rh-Carbynoids DOI Creative Commons
Hang‐Fei Tu, Aliénor Jeandin, Marcos G. Suero

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(37), P. 16737 - 16743

Published: Sept. 8, 2022

Herein, we report the first catalytic one-step synthesis of cyclopropenium cations (CPCs) with readily available alkynes and hypervalent iodine reagents as carbyne sources. Key to process is generation a novel Rh-carbynoid that formally transfers monovalent cationic carbynes (:+C-R) via an oxidative [2+1] cycloaddition. Our able synthesize new type CPC substituted ester group underpins regioselective attack broad range carbon heteroatomic nucleophiles, thus providing platform for valuable cyclopropenes difficult or not possible make by current methodologies.

Language: Английский

Citations

31