Upgrading ketone synthesis direct from carboxylic acids and organohalides DOI Creative Commons

Rehanguli Ruzi,

Kai Liu, Chengjian Zhu

et al.

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: July 3, 2020

Abstract The ketone functional group has a unique reactivity in organic chemistry and is associated with number of useful reactions. Catalytic methods for synthesis are continually being developed. Here, we report photoredox, nickel phosphoranyl radical synergistic cross-electrophile coupling commercially available chemicals, aromatic acids aryl/alkyl bromides. This allows concise highly functionalized ketones directly, without the preparation activated carbonyl intermediates or organometallic compounds, thus complements conventional Weinreb synthesis. Use appropriate photocatalyst, ligand amount solvents can match reaction rate required by any simple catalytic cycle. practicality synthetic robustness illustrated facile complex from readily feedstock chemicals.

Language: Английский

Decarbonylative Cyanation of Amides by Palladium Catalysis DOI
Shicheng Shi, Michal Szostak

Organic Letters, Journal Year: 2017, Volume and Issue: 19(12), P. 3095 - 3098

Published: June 1, 2017

Transition-metal-catalyzed cyanation of aryl halides is a process significant importance in the preparation pharmaceuticals, organic materials and agrochemicals. Here, we demonstrate palladium-catalyzed decarbonylative amides by highly selective carbon-nitrogen bond cleavage for synthesis wide range nitriles. The utility this technology demonstrated isotopically labeled nitriles orthogonal cross-coupling reactions bench-stable to establish synthons with opposite polarity.

Language: Английский

Citations

100
[Pd(NHC)(acac)Cl]: Well-Defined, Air-Stable, and Readily Available Precatalysts for Suzuki and Buchwald–Hartwig Cross-coupling (Transamidation) of Amides and Esters by N–C/O–C Activation DOI
Tongliang Zhou, Guangchen Li, Steven P. Nolan

et al.

Organic Letters, Journal Year: 2019, Volume and Issue: 21(9), P. 3304 - 3309

Published: April 16, 2019

A general class of well-defined, air-stable, and readily available Pd(II)-NHC precatalysts (NHC = N-heterocyclic carbene) for Suzuki Buchwald–Hartwig cross-coupling amides (transamidation) esters by selective N–C/O–C cleavage is reported. Since these are highly active the easiest to synthesize, study clearly suggests that [Pd(NHC)(acac)Cl] should be routinely included during development new methods. An assay in situ screening NHC salts this manifold presented.

Language: Английский

Citations

100
Nickel-Catalyzed C–O Bond-Cleaving Alkylation of Esters: Direct Replacement of the Ester Moiety by Functionalized Alkyl Chains DOI
Xiangqian Liu, Jiaqi Jia, Magnus Rueping

et al.

ACS Catalysis, Journal Year: 2017, Volume and Issue: 7(7), P. 4491 - 4496

Published: June 7, 2017

Two efficient protocols for the nickel-catalyzed aryl–alkyl cross-coupling reactions using esters as coupling components have been established. The methods enable selective oxidative addition of nickel to acyl C–O and aryl bonds allow via decarbonylative bond cleavage or through a with high efficiency good functional group compatibility. streamlined, unconventional utilization widespread ester groups their precursors, carboxylic acids phenols, in synthetic organic chemistry.

Language: Английский

Citations

96
Nickel-Catalyzed Suzuki–Miyaura Coupling of Aliphatic Amides DOI
Timothy B. Boit, Nicholas A. Weires, Junyong Kim

et al.

ACS Catalysis, Journal Year: 2017, Volume and Issue: 8(2), P. 1003 - 1008

Published: Dec. 20, 2017

We report the Ni-catalyzed Suzuki–Miyaura coupling of aliphatic amide derivatives. Prior studies have shown that derivatives can undergo carbon–heteroatom bond formation but Ni-mediated C–C using has remained difficult. The disclosed herein is tolerant considerable variation with respect to both amide-based substrate and boronate partner proceeds in presence heterocycles epimerizable stereocenters. Moreover, a gram-scale coupling/Fischer indolization sequence demonstrates ease which unique polyheterocyclic scaffolds be constructed, particularly by taking advantage enolizable ketone functionality present cross-coupled product. methodology provides an efficient means form bonds from nonprecious-metal catalysis offers general platform for heteroarylation acyl electrophiles.

Language: Английский

Citations

95
Upgrading ketone synthesis direct from carboxylic acids and organohalides DOI Creative Commons

Rehanguli Ruzi,

Kai Liu, Chengjian Zhu

et al.

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: July 3, 2020

Abstract The ketone functional group has a unique reactivity in organic chemistry and is associated with number of useful reactions. Catalytic methods for synthesis are continually being developed. Here, we report photoredox, nickel phosphoranyl radical synergistic cross-electrophile coupling commercially available chemicals, aromatic acids aryl/alkyl bromides. This allows concise highly functionalized ketones directly, without the preparation activated carbonyl intermediates or organometallic compounds, thus complements conventional Weinreb synthesis. Use appropriate photocatalyst, ligand amount solvents can match reaction rate required by any simple catalytic cycle. practicality synthetic robustness illustrated facile complex from readily feedstock chemicals.

Language: Английский

Citations

95