Aminocarbonylation Reaction Using a Pd–Sn Heterobimetallic Catalyst: Three-Component Coupling for Direct Access of the Amide Functionality DOI
Anuradha Mohanty,

Soheli Sadhukhan,

Mukesh Kumar Nayak

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(2), P. 1010 - 1017

Published: Jan. 6, 2024

A heterobimetallic "Pd–Sn" catalyst, namely, PdCl(PPh3)2SnCl3, efficiently catalyzes the aminocarbonylation reaction of aryl iodides with amines under atmospheric pressure CO in absence a base and additive. Primary, secondary, alkyl all afforded corresponding amides good to excellent yields high selectivity. broad range functional groups were tolerated. The method was further extended synthesis biologically active isoindoline-1,3-diones presence triethylamine. mechanism is proposed for reaction.

Language: Английский

Generation and transformation of α-oxy carbene intermediates enabled by copper-catalyzed carbonylation DOI Creative Commons
Yang Yuan, Xiao‐Feng Wu

Green Carbon, Journal Year: 2024, Volume and Issue: 2(1), P. 70 - 80

Published: Jan. 11, 2024

Since the Fischer-Tropsch reaction was discovered by Otto Roelen in 1938, transition metal-catalyzed carbonylation reactions come as one of most important methods for preparing carbonyl-containing and carbon chain-increased compounds. As a result, field research has received considerable attention over past decades continues to increase. With continuous development in-depth study mechanism, more mechanistic details variations have been revealed, which provide possibilities organic synthesis. Recently, copper catalysis introduced carbonylative functionalization alkenes, thus enabling rapid assembly functionalized carbonyl compounds from simple starting materials. In this Account, we summarize new findings Cu-catalyzed borocarbonylation alkenes based on generation transformation α-oxy carbene intermediates. We believe that results presented Account will further inspire design reactions.

Language: Английский

Citations

24
Palladium-Catalyzed Carbonylations: Application in Complex Natural Product Total Synthesis and Recent Developments DOI Creative Commons
Hunter S. Sims, Mingji Dai

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(8), P. 4925 - 4941

Published: Jan. 27, 2023

Carbon monoxide is a cheap and abundant C1 building block that can be readily incorporated into organic molecules to rapidly build structural complexity. In this Perspective, we outline several recent (since 2015) examples of palladium-catalyzed carbonylations in streamlining complex natural product total synthesis highlight the strategic importance these carbonylation reactions corresponding synthesis. The selected include spinosyn A, callyspongiolide, perseanol, schizozygane alkaloids, cephanolides, bisdehydroneostemoninine related stemona alkaloids. We also provide our perspective about advancements future developments carbonylations.

Language: Английский

Citations

39
Light-Mediated Synthesis of Aliphatic Anhydrides by Cu-Catalyzed Carbonylation of Alkyl Halides DOI

Pinku Tung,

Neal P. Mankad

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(17), P. 9423 - 9427

Published: April 19, 2023

Acid anhydrides are valuable in the chemical industry for their role synthesizing polymers, pharmaceuticals, and other commodities, but syntheses often involve multiple steps with precious metal catalysts. The simplest anhydride, acetic is currently produced by two Rh-catalyzed carbonylation reactions on a bulk scale its use products ranging from aspirin to cellulose acetate. Here, we report light-mediated, Cu-catalyzed process producing aliphatic, symmetric acid directly of alkyl (pseudo)halides single step without any additives. transformation requires only simple Cu salts abundant bases generate heterogeneous Cu0 photocatalyst situ, maintains high efficiency selectivity upon scale-up, operates radical mechanism several beneficial features. This discovery will enable engineering processes commodity efficiently sustainably.

Language: Английский

Citations

25
Nickel-Catalyzed Carbonylative Negishi Cross-Coupling of Unactivated Secondary Alkyl Electrophiles with 1 atm CO Gas DOI

Yetong Zhang,

Qihang Cao,

Yang Xi

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7971 - 7978

Published: March 14, 2024

We describe a nickel-catalyzed carbonylative cross-coupling of unactivated secondary alkyl electrophiles with the organozinc reagent at atmospheric CO gas, thus allowing expedient construction unsymmetric dialkyl ketones broad functional group tolerance. The leverage newly developed

Language: Английский

Citations

15
Carbonylative transformation of aryl halides and strong bonds via cheap metal catalysts and sustainable technologies DOI Creative Commons
Maolin Yang, Yukun Liu, Xin Qi

et al.

Green Synthesis and Catalysis, Journal Year: 2024, Volume and Issue: 5(4), P. 211 - 269

Published: May 6, 2024

The development of catalytic carbonylation reactions has increased considerably. Although many reviews/chapters/books on have been published, summaries cheap metal-catalyzed aryl halides and other chemical bonds with high dissociation energy C-Y (Y = O, N, H) are still very rare. Focusing green sustainable chemistry, this review summarizes discusses the achievements carbonylative transformations (C(sp2)-X) strong based non-expensive metal catalysts (Co, Mn, Mo, Ni, Fe, Cu), photochemical electrochemical systems developed in recent decades.

Language: Английский

Citations

14
Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization DOI
Xinghua Wang,

J. P. He,

Yanan Wang

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

Citations

12
Synchronous recognition of amines in oxidative carbonylation toward unsymmetrical ureas DOI

Jinhui Wang,

Shengchun Wang, Zhihong Wei

et al.

Science, Journal Year: 2024, Volume and Issue: 386(6723), P. 776 - 782

Published: Nov. 14, 2024

Unsymmetrical ureas are commonly found in pharmaceuticals and bioactive compounds. However, devising strategies to introduce two distinct amines selectively the construction of unsymmetrical remains a challenge. In this work, we use synchronous recognition strategy that takes advantage radical nucleophilic activation discriminate between secondary primary amines. Specifically, copper catalyst preferentially oxidizes species, whereas cobalt carbonylates produce amides. Coupling these fragments by cooperative catalysis produces with high selectivity, as showcased modification 41 biologically active compounds six drugs.

Language: Английский

Citations

11
Copper‐Catalyzed 1,2‐Trifluoromethylation Carbonylation of Unactivated Alkenes: Efficient Access to β‐Trifluoromethylated Aliphatic Carboxylic Acid Derivatives DOI
Fu‐Peng Wu, Yang Yuan, Xiao‐Feng Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(49), P. 25787 - 25792

Published: Oct. 9, 2021

A novel copper-catalyzed carbonylative trifluoromethylation of unactivated alkenes has been developed. broad range β-trifluoromethylated carboxylic acid derivatives were prepared in moderate to excellent yields from simple with regioselectivity. It is noteworthy that ethylene gas, as the simplest olefin, can also be applied directly obtain amides and ester. This transformation presents first example on alkenes.

Language: Английский

Citations

52
Iron‐Catalyzed Alkoxycarbonylation of Alkyl Bromides via a Two‐Electron Transfer Process DOI
Han‐Jun Ai,

Benedict N. Leidecker,

Phong Dam

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(43)

Published: Sept. 8, 2022

Transition metal-catalyzed carbonylative cross-coupling reactions are some of the most widely used methods in organic synthesis. However, despite obvious advantages iron as an abundant and low toxicity transition metal catalyst, its practical application carbonylation reaction remains largely unexplored. Here we report our recent study on Fe-catalyzed alkoxycarbonylation alkyl halides. Mechanistic studies indicate that is catalyzed by situ generated Fe2- complex. This low-valent species activates bromides via a distinctive two-electron transfer (TET) process, whereas it proceeds single electron (SET) process for iodides which consistent with literature.

Language: Английский

Citations

31
Copper‐Catalyzed 1,2‐Dicarbonylative Cyclization of Alkenes with Alkyl Bromides via Radical Cascade Process DOI Creative Commons
Fengqian Zhao,

Xing‐Wei Gu,

Robert Franke

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(49)

Published: Oct. 18, 2022

Herein, we developed a new procedure on 1,2-dicarbonylative cyclization of 4-aryl-1-butenes with alkyl bromides. Using simple copper catalyst, two molecules carbon monoxide were introduced into the double bond formation four C-C bonds and ring. Various α-tetralones 2,3-dihydroquinolin-4-ones formed in moderate to good yields.

Language: Английский

Citations

29