Enantioselective Hydrocarbamoylation of Alkenes DOI Creative Commons
Sheng Feng, Yuyang Dong, Stephen L. Buchwald

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: June 3, 2022

The asymmetric hydroaminocarbonylation of olefins represents a straightforward approach for the synthesis enantioenriched amides, but is hampered by necessity to employ CO gas, often at elevated pressures. We herein describe, as an alternative, enantioselective hydrocarbamoylation alkenes leveraging dual copper hydride and palladium catalysis enable use readily available carbamoyl chlorides practical carbamoylating reagent. protocol applicable various types olefins, including alkenyl arenes, terminal alkenes, 1,1-disubstituted alkenes. Substrates containing diverse range functional groups well heterocyclic substructures undergo functionalization provide α- β-chiral amides in good yields with excellent enantioselectivities.

Language: Английский

Contemporary Approaches for Amide Bond Formation DOI
Paola Acosta‐Guzmán, Andrea Ojeda‐Porras, Diego Gamba‐Sánchez

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4359 - 4391

Published: Nov. 7, 2023

Abstract Amide bond construction has garnered significant interest in recent decades due to amides being one of the most prevalent functional groups among bioactive molecules. Out thirty‐seven new drugs approved by FDA 2022, eleven are small molecules containing at least amide bond. Additionally, there nineteen large as drugs, some which have peptide structures, and therefore, also bear bonds. In years, multiple teams embraced challenge developing more efficient methods for formation. This dedication led numerous publications appearing monthly prestigious journals, showcasing advancements this field. The primary goal review is present viable strategies constructing It crucial differentiate between formation synthesis; hence, focus on describing specific forming C(O)−N particular, concentrates developed within last six years. There a particular emphasis approaches that consider thought process when selecting starting materials groups. approach ensures coverage all common chemical transformations yield

Language: Английский

Citations

48
Cobalt-catalyzed synthesis of amides from alkenes and amines promoted by light DOI
Mason S. Faculak, Alexander M. Veatch, Erik J. Alexanian

et al.

Science, Journal Year: 2024, Volume and Issue: 383(6678), P. 77 - 81

Published: Jan. 4, 2024

Catalytic methods to couple alkene and amine feedstocks are valuable in synthetic chemistry. The direct carbonylative coupling of alkenes amines holds promise as a perfectly atom-economical approach amide synthesis, but general remain underdeveloped. Herein, we report an hydroaminocarbonylation catalyzed by unmodified, inexpensive cobalt carbonyl under mild conditions low pressure promoted light. Silane addition after the reaction enables sequential cobalt-catalyzed reduction, constituting formal hydroaminomethylation. These exhibit exceptional scope across both components with high chemo- regioselectivity proceed efficiently even absence solvent. formation hydridocobalt through photodissociation ligand is proposed enable catalytic activity conditions, which addresses long-standing challenge catalysis.

Language: Английский

Citations

23
Palladium‐Catalyzed Asymmetric Markovnikov Hydroxycarbonylation and Hydroalkoxycarbonylation of Vinyl Arenes: Synthesis of 2‐Arylpropanoic Acids DOI

Ya‐Hong Yao,

Xian‐Jin Zou,

Yuan Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(43), P. 23117 - 23122

Published: July 9, 2021

Abstract Asymmetric hydroxycarbonylation is one of the most fundamental yet challenging methods for synthesis carboxylic acids. Herein, we reported development a palladium‐catalyzed highly enantioselective Markovnikov vinyl arenes with CO and water. A monodentate phosphoramidite ligand L6 plays vital role in reaction. The reaction tolerates range functional groups, provides facile atom‐economical approach to an array 2‐arylpropanoic acids including several commonly used non‐steroidal anti‐inflammatory drugs. catalytic system has also enabled asymmetric hydroalkoxycarbonylation alcohols afford 2‐arylpropanates. Mechanistic investigations suggested that hydropalladation irreversible regio‐ enantiodetermining step, while hydrolysis/alcoholysis probably rate‐limiting step.

Language: Английский

Citations

67
Regioselective and Enantioselective Copper‐Catalyzed Hydroaminocarbonylation of Unactivated Alkenes and Alkynes DOI Creative Commons
Yang Yuan, Youcan Zhang, Wenbo Li

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 16, 2023

Given the prevalence of amide backbones in marketed pharmaceuticals and their ubiquity as critical binding units natural peptides proteins, it remains important to develop novel methods construct bonds. We report here a general method for anti-Markovnikov hydroaminocarbonylation unactivated alkenes under mild conditions, using copper catalysis combination with hydroxylamine electrophile reagents poly(methylhydrosiloxane) (PMHS) cheap environmentally friendly hydride source. The reaction tolerates variety functional groups efficiently converts terminal alkenes, 1,1-disubstituted cyclic corresponding amides exclusive selectivity (and high enantioselectivities/diastereoselectivities). Additionally, minimal modification alkynes can also undergo tandem hydrogenation-hydroaminocarbonylation alkyl amides.

Language: Английский

Citations

23
Palladium‐Catalyzed Inward Isomerization Hydroaminocarbonylation of Alkenes DOI

Xian‐Jin Zou,

Zhao‐Xing Jin,

Huiyi Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)

Published: April 15, 2024

In contrast to the kinetically favored outward isomerization-hydrocarbonylation of alkenes, disfavored inward alkenes remains an important challenge. Herein, we have developed a novel and effective palladium-catalyzed isomerization-hydroaminocarbonylation unactivated aniline hydrochlorides for formation synthetically valuable α-aryl carboxylic amides in high yields site-selectivities. The efficiency reaction is attributed relay catalysis strategy, which Markovnikov-favored [PdH]-P

Language: Английский

Citations

11
Recent Advances in Mono‐ and Difunctionalization of Unactivated Olefins DOI

Monak Patel,

Bhargav Desai, Aakash Sheth

et al.

Asian Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 10(12), P. 3201 - 3232

Published: Nov. 5, 2021

Abstract Olefins are synthetically useful building blocks in modern organic synthesis. Direct functionalization of olefins; represent one the most explored transformations synthetic chemistry due to their easy availability and reactivity towards large number reactants affording diverse range compounds. In recent times, development new protocols for olefins is a growing realm. A plethora olefin methodologies have been reported literature through ionic free radical mechanisms including single electron transfer (SET) last two decades. This review gives an overview mono‐ difunctionalization unactivated olefins, with emphasis on mechanistic details.

Language: Английский

Citations

52
Molecular hard-segment engineered polyurethane with thermochromism, shape memory, humidity-driven, and self-healing capabilities DOI
Naqi Li, Zhishuai Cui, Xiaolei Yue

et al.

Sensors and Actuators B Chemical, Journal Year: 2024, Volume and Issue: 404, P. 135266 - 135266

Published: Jan. 4, 2024

Language: Английский

Citations

8
Synthesis of Cycloaliphatic Polyamides via Palladium-Catalyzed Hydroaminocarbonylative Polymerization DOI

Yaodu Zhang,

Fei Wu,

Huiyi Yang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 12883 - 12888

Published: May 6, 2024

Polyamides represent one class of materials that is important in modern society. Because the numerous potential applications polyamides various fields, there a high demand for new polyamide structures, which necessitates development polymerization methods. Herein, we report novel and efficient palladium-catalyzed hydroaminocarbonylative dienes diamines synthesis cycloaliphatic polyamides. The method employs readily available starting materials, proceeds an atom-economic manner, creates series functional yields molecular weights. In contrast with traditional based on adipic acid, have superior thermal resistance, higher glass-transition temperature, better solubility common organic solvents, thus probably featuring merits high-performance good processability.

Language: Английский

Citations

8
Mechanochemical Divergent Syntheses of Oxindoles and α‐Arylacylamides via Controllable Construction of C−C and C−N Bonds by Copper and Piezoelectric Materials DOI

Honggui Lv,

Xinyue Xu, Jing Li

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(34)

Published: June 29, 2022

Abstract Herein, we present the divergent syntheses of α‐arylacylamides and oxindoles via mechanoredox chemistry by using easily accessible α‐bromo N ‐sulfonyl amides as starting materials. Our system consists a catalytic amount Cu II precatalyst piezoelectric The highly polarized BaTiO 3 or PbTiO under mechanical agitation can act an electron donor to realize recycling I . Control experiments density functional theory calculations have been performed support proposed mechanistic rationale for cascade reactions.

Language: Английский

Citations

28
Palladium-catalyzed regiodivergent hydrochlorocarbonylation of alkenes for formation of acid chlorides DOI Creative Commons

Fei Wu,

Bo Wang, Naqi Li

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 31, 2023

Novel strategy for acid chlorides formation that do not use carboxylic acids is particularly attractive in chemical synthesis but remains challenging. Herein, we reported the development of a highly effective Pd-catalyzed hydrochlorocarbonylation alkenes with CO alkyl chlorides. Chlorosilane and AcOH were found as mild HCl source reaction. The reaction shows broad substrate scope produces both branched linear good to high yields upon different ligands solvents. Cooperating follow-up acylation reactions, offers complementary platform diverse carbonyl compounds from alkenes. Mechanistic investigations suggested proceeded though palladium hydride pathway, prompted reductive elimination acyl-Pd-Cl intermediate.

Language: Английский

Citations

16