Copper-Catalyzed 1,2-Difunctionalization Trifluoromethylamidation of Alkynes Assisted by a Coordinating Group DOI
Jing Ren, Kaiyun Liu, Ning Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(16), P. 11001 - 11011

Published: Aug. 4, 2023

The radical 1,2-difunctionalization reaction of alkynes has evolved into a versatile approach to multisubstituted alkylenes. However, robust catalytic strategies perform carboamination are lacking, despite the ubiquity resulting enamines in natural molecules, bioactive and pharmaceutical compounds. Herein, we show that bidentate coordinating group judiciously installed on amines could act as an efficient tool for enabling trifluoromethylamidation alkynes. This strategy exhibits broad substrate scope with good functional compatibility is amenable late-stage functionalization compounds biologically relevant motifs, allowing straightforward synthesis large library CF3-containing enamides, high-value pharmacophores, single step from readily accessible amides, Langlois' reagent, current methodology can also be successfully extended difluoromethylamidation Additionally, various mechanistic experiments, such competition H/D isotopic exchanging trap Hammett studies, kinetic have been performed better understanding mechanism.

Language: Английский

Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes DOI Creative Commons
Tianyu Long, Chen Zhu, Ling Li

et al.

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

Published: Jan. 4, 2023

Precise stereocontrol of functionalized alkenes represents a long-standing research topic in organic synthesis. Nevertheless, the development catalytic, easily tunable synthetic approach for stereodivergent synthesis both E-selective and even more challenging Z-selective highly substituted 1,3-dienes from common substrates remains underexploited. Here, we report photoredox nickel dual catalytic strategy sulfonylalkenylation terminal alkynes with vinyl triflates sodium sulfinates under mild conditions. With judicious choice simple catalyst ligand, this method enables efficient divergent access to Z- E-sulfonyl-1,3-dienes same set starting materials. This features broad substrate scope, good functional compatibility, excellent chemo-, regio-, stereoselectivity. Experimental DFT mechanistic studies offer insights into observed stereoselectivity controlled by ligands.

Language: Английский

Citations

50
Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes DOI
Pu‐Fan Qian, Tao Zhou, Bing‐Feng Shi

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(85), P. 12669 - 12684

Published: Jan. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Language: Английский

Citations

42
E/Z Photoisomerization of Olefins as an Emergent Strategy for the Control of Stereodivergence in Catalysis DOI Creative Commons
Javier Corpas, Pablo Mauleón, Ramón Goméz Arrayás

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(8), P. 1348 - 1370

Published: March 5, 2022

Abstract The stereoselective photoisomerization of olefins via Energy Transfer (E n T) sensitization bears significant potential in the context rational design catalytic stereodivergent methodologies. Whereas approaches for controlling access to E‐ and Z ‐ isomers depend highly on nature catalyst – therefore are not easily implemented as a general strategy E T catalysis has emerged recent years an increasingly powerful tool olefin geometry control nearly perfect step‐economic fashion. Moreover, this approach presents both high functional group tolerance and, most notably, demonstrated ample multicatalytic compatibility. This feature enabled development tandem strategies, which focus Review. magnified image

Language: Английский

Citations

45
Recent Advances in the Functionalization of Terminal and Internal Alkynes DOI

Arti Ramani,

Bhargav Desai,

Monak Patel

et al.

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(5)

Published: March 9, 2022

Abstract Alkynes are one of the most fundamental and diverse functional groups utilized in organic synthesis. Over past few years, development efficient synthetic methodologies for functionalization alkynes has been an active area research. A plethora alkyne reactions have reported literature to construct functionalized alkene scaffolds, which important building blocks many natural products, pharmaceuticals, key intermediates various transformations. In this review, we describe recent advances with emphasis on substrate scope, limitations, regioselectivity control applications these reactions. This review covers from 2016 2021.

Language: Английский

Citations

43
Nickel‐Catalyzed Defluorinative Asymmetric Cyclization of Fluoroalkyl‐Substituted 1,6‐Enynes for the Synthesis of Seletracetam DOI

Kuai Wang,

Jiachang Chen, Wenfeng Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 23, 2022

Abstract The introduction of fluorine‐containing groups into organic molecules can significantly affect their physical and chemical properties has long been used as an effective strategy for drug discovery development. Consequently, the development catalytic asymmetric methods synthesis heterocycles is highly desirable sought after. Herein, we describe a nickel‐catalyzed defluorinative cyclization fluoroalkyl‐substituted 1,6‐enynes, providing expedient access to synthetically attractive 4‐fluorovinyl‐substituted 2‐pyrrolidones in good yields with remarkable high levels chemo‐, regio‐, enantioselectivities (90–99 % ee,>35 examples). This protocol features readily available starting materials excellent functional group compatibility, exhibits complementary regioselectivity. utility this was demonstrated enantioselective antiepileptic Seletracetam.

Language: Английский

Citations

41
Photoinduced difunctionalization with bifunctional reagents containing N-heteroaryl moieties DOI
Wooseok Lee, Inyoung Park, Sungwoo Hong

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(6), P. 1688 - 1700

Published: May 10, 2023

Language: Английский

Citations

28
Nickel-catalyzed switchable arylative/endo-cyclization of 1,6-enynes DOI Creative Commons
Wenfeng Liu, Wei Li,

Weipeng Xu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: April 4, 2024

Abstract Carbo- and heterocycles are frequently used as crucial scaffolds in natural products, fine chemicals, biologically pharmaceutically active compounds. Transition-metal-catalyzed cyclization of 1,6-enynes has emerged a powerful strategy for constructing functionalized carbo- heterocycles. Despite significant progress, the regioselectivity alkyne functionalization is entirely substrate-dependent. And only exo -cyclization/cross-coupling products can be obtained, while endo -selective cyclization/cross-coupling remains elusive still poses formidable challenge. In this study, we disclose nickel-catalyzed switchable arylation/cyclization which nature ligand dictates arylation, electrophilic trapping reagents determine selectivity mode. Specifically, using commercially available 1,10-phenanthroline facilitates trans -arylation/cyclization to obtain seven-membered ring 2-naphthyl-substituted bisbox promotes cis access six-membered products. Diastereoselective cyclizations have also been developed synthesis enantioenriched piperidines azepanes, core structural elements pharmaceuticals possessing important biological activities. Furthermore, experimental density functional theory studies reveal that arylation process controlled by steric hindrance ligand; reaction mechanism involves -cyclization followed Dowd-Beckwith-type expansion form

Language: Английский

Citations

12
Energy-Transfer-Enabled Radical Acylation Using Free Alkyl Boronic Acids through Photo and NHC Dual Catalysis DOI

Wan-Cong Liu,

Xiang Zhang, Lin Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3181 - 3190

Published: Feb. 14, 2024

Cross-coupling reactions have been well received as one of the most popular protocols for ketone synthesis. As an important coupling partner, bench-stable and commercially available alkyl boronic acids are widely used in transition metal catalysis, but they rarely utilized radical precursors acylative reactions. Herein, we reported energy-transfer-enabled acylation using free via NHC/photo dual catalysis. This protocol could efficiently promote Suzuki-type cross-coupling between acyl imidazoles multicomponent alkylacylations alkenes, thus producing various ketones with structural diversity. Additionally, products can readily transform into a large number structurally interesting fine chemicals. Preliminary mechanistic studies shed light on unique reaction mechanism.

Language: Английский

Citations

10
Reversible Radical Addition Guides Selective Photocatalytic Intermolecular Thiol‐Yne‐Ene Molecular Assembly DOI
Nikita S. Shlapakov, Andrey D. Kobelev, Julia V. Burykina

et al.

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

Published: Jan. 19, 2024

Abstract In modern organic chemistry, harnessing the power of multicomponent radical reactions presents both significant challenges and extraordinary potential. This article delves into this scientific frontier by addressing critical issue controlling selectivity in such complex processes. We introduce a novel approach that revolves around reversible addition thiyl radicals to multiple bonds, reshaping landscape reactions. The key lies intricate interplay between reversibility energy landscapes governing C−C bond formation thiol‐yne‐ene developed not only allows prioritize cascade, dominating over alternative reactions, but also extends scope coupling products obtained from alkenes alkynes various structures electron density distributions, regardless their relative polarity difference, opening doors more versatile synthetic possibilities. present study, we provide powerful tool for atom‐economical C−S formation, paving way efficient synthesis molecules. Carrying out our experimental computational studies, elucidated fundamental mechanisms underlying cascades, knowledge can be broadly applied field chemistry.

Language: Английский

Citations

9
Photocatalytic Reductive Functionalization of Aryl Alkynes via Alkyne Radical Anions DOI
Xiaogang Tong, Zugen Wu, Hwee Ting Ang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9283 - 9293

Published: June 4, 2024

The direct reductive functionalization of alkynes under mild conditions presents a promising yet challenging avenue for accessing value-added molecules. Alkyne radical anions represent distinct class reactive intermediates characterized by both charge and an unpaired electron, thus holding great potential facilitating diverse bond formations, particularly in alkyne functionalization. However, the synthetic utility is limited, primarily due to difficulty their generation formation highly unstable vinyl intermediates. In this study, we accomplished from aryl feedstocks via single electron transfer (SET) reduction with photogenerated CO2 anion (CO2•–), enabling hydroalkylation, arylalkenylation, hydrocarboxylation alkynes. Our photocatalytic strategy features metal-free catalysis, reaction conditions, employment traceless reductant, good functional group compatibility, step- atom-economy, high regioselectivity. This study not only paves way leveraging underexplored but also catalyzes ongoing exploration bifunctional CO2•– species chemistry.

Language: Английский

Citations

9