Mechanistic Insights into Enantioselective C(sp3)−H Acylation to Construct α‐Amino Ketones via Photoredox and Ni(II) Dual Catalysis: A DFT Study DOI
Ran Liu, Kang Lv, Xiaoguang Bao

et al.

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(8)

Published: March 5, 2023

The development of the merger a Ni(II) catalyst with an appropriate photocatalyst under visible-light irradiation provides new strategy for realizing direct functionalization C(sp3 )-H bonds. Mechanistically, whether reduction Ni to form Ni(0) species is necessary in dual catalysis still remains debate. Herein, DFT calculations were carried out gain mechanistic insight into enantioselective acylation α-amino bonds furnish ketones via photoredox and catalysis. A feasible pathway Ni(I)-Ni(III)-Ni(II)-Ni(III)-Ni(I) cycle suggested sequential elementary steps oxidative addition, single electron reduction, radical reductive elimination leading final product, whereas nickel catalytic cycle, Ni(I)-Ni(0)-Ni(II)-Ni(III)-Ni(I), might not be dual-catalyzed origin stereoselectivity this reaction also discussed, which could attributed minimization steric hindrance between alkyl moiety part phenyl group chiral ligand.

Language: Английский

Synthesis of 1-perfluoroalkyl-3-heteroaryl bicyclo[1.1.1]pentanes via visible light-induced and metal-free perfluoroalkylation of [1.1.1]propellane DOI

Boan Yan,

Gongcheng Xu,

Hang Han

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(5), P. 1948 - 1954

Published: Jan. 1, 2023

Visible light-induced perfluoroalkylation of [1.1.1]propellane provides a sustainable way to incorporate perfluoroalkyl-substituted BCPs into various heterocycles.

Language: Английский

Citations

37
Visible‐Light‐Promoted Electron Donor‐Acceptor Complex Enabled Decarboxylative Alkylation of Quinoxalin‐2(1H)‐ones and N‐Hydroxyphthalimide Esters with Na2S as a Catalytic Donor DOI

Hai‐Yang Song,

Zhuo‐Tao Zhang,

Hong‐Yu Tan

et al.

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(2)

Published: Jan. 11, 2023

Abstract We developed a novel and efficient method for the synthesis of various 3‐alkylated quinoxalin‐2(1 H )‐ones (32 examples, 70%–96% yields) through electron donor‐acceptor complex enabled alkylation with N ‐ hydroxyphthalimide esters as alkyl source Na 2 S catalytic donor under external photocatalyst‐, oxidant‐ additive‐free conditions.

Language: Английский

Citations

22
NiH-Catalyzed Regio- and Enantioselective Hydroalkylation for the Synthesis of β- or γ-Branched Chiral Aromatic N-Heterocycles DOI
Ju‐Song Yang,

Ka Lu,

Chen‐Xiao Li

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(40), P. 22122 - 22134

Published: Sept. 25, 2023

A nickel hydride-catalyzed regio- and enantioselective hydroalkylation reaction was developed to give access a library of chiral β- or γ-branched aromatic N-heterocycles. This intriguing asymmetric transformation features excellent selectivities, step- atom-economies, generating two kinds products through one synthetic strategy. Furthermore, the possible mechanism extensively investigated using numerous control experiments density functional theory calculations.

Language: Английский

Citations

21
Applications of Hantzsch Esters in Organocatalytic Enantioselective Synthesis DOI Open Access
Ana Maria Faísca Phillips, Armando J. L. Pombeiro

Catalysts, Journal Year: 2023, Volume and Issue: 13(2), P. 419 - 419

Published: Feb. 16, 2023

Hantzsch esters (1,4-dihydropyridine dicarboxylates) have become, in this century, very versatile reagents for enantioselective organic transformations. They can act as hydride transfer agents to reduce, regioselectively, a variety of multiple bonds, e.g., C=C and C=N, under mild reaction conditions. are excellent the dearomatization heteroaromatic substances, participate readily cascade processes. In last few years, they also become useful photoredox reactions. sacrificial electron hydrogen donors when 4-alkyl or 4-acyl-substituted, alkyl acyl radical agents. These reactions may take place presence absence photocatalyst. This review surveys literature published area five years.

Language: Английский

Citations

18
Quinone-Initiated Photocatalytic Enantioselective Giese Radical Addition with Ethers, Thioethers, Amines, and Alkanes DOI
Yao Luo, Yuqiao Zhou,

Fengnan Xiao

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12031 - 12041

Published: July 29, 2024

Photocatalytic enantioselective Giese radical addition with inert C(sp3)–H bonds represents a highly efficient and economically favorable approach to synthesizing diverse value-added chiral molecules from abundant feedstock. Herein, we disclose quinone-initiated photocatalytic asymmetric of α-substituted acrylamides by applying simple quinones as HAT photocatalysts in combination N,N′-dioxide/praseodymium(III) catalyst. A wide array ethers, thioethers, selenide, amines, alkanes can smoothly transform into the corresponding α-aryl amide derivatives satisfactory enantioselectivities (68 examples, up 95% ee) under mild conditions. Based on spectroscopy studies control experiments, catalytic cycle was proposed, DFT calculations revealed that interaction between quinone Lewis acid essential for enantio-induction back hydrogen atom transfer process.

Language: Английский

Citations

6
Enantioselective Giese Additions of Prochiral α-Amino Radicals DOI Creative Commons
Antti S. K. Lahdenperä, P. David Bacoş, Robert J. Phipps

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(49), P. 22451 - 22457

Published: Dec. 1, 2022

Amines featuring an adjacent stereocenter are important building blocks, and recent years have seen remarkable growth in methods forming these via prochiral α-amino radical intermediates. However, very few can exert control over the newly formed stereocenter. We disclose a strategy to overcome this context of one most widely used carbon–carbon bond reactions, Giese reaction. Incorporation removable basic heteroarene into substrate enables network attractive noncovalent interactions between phosphoric acid catalyst, subsequently radical, acceptor, allowing catalyst during C–C step. Deprotection products leads analogues γ-aminobutyric acid. anticipate that will be applicable other asymmetric transformations which is presently challenging.

Language: Английский

Citations

21
Catalytic enantioselective synthesis of α-C chiral sulfones enabled by merging photoactive electron donor-acceptor complexes with nickel catalysis DOI Creative Commons

Zemin Lai,

Ying Xie, Lele Huang

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: 16(10), P. 4352 - 4359

Published: Jan. 1, 2025

α-C chiral sulfones are privileged building blocks widely found in pharmaceuticals, agrochemicals, natural products, and ligands. Although many nucleophilic or electrophilic protocols have been developed for their construction, radical-based asymmetric catalysis, especially that involving photoactive electron donor-acceptor (EDA) complexes, remains a significant unmet challenge. Herein, we present the first catalytic production of enabled by merging EDA complex with Ni catalyst. With this cooperative catalysis system, wide range achieved good yields excellent enantioselectivities (53 examples, up to 99% yield, 99 : 1 er). The synthetic utility protocol is further demonstrated synthesis selective MMP-3 (stromelysin-1) inhibitor. Detailed mechanistic spectroscopic studies suggest newly identified type generated from sulfonyl chlorides Hantzsch esters (HEs) crucial success as precursor radicals.

Language: Английский

Citations

0
Kinetic Resolution of Racemic Radicals in Asymmetric Photoredox Minisci Reactions with Azaarenes for Precise Construction of Two Non-adjacent Stereocenters DOI
Tianju Shao,

Feiyun Nie,

Shanshan Cao

et al.

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

Published: March 11, 2025

Despite the significant potential of photocatalysis as a robust synthetic tool, high reactivity radicals often presents challenges in achieving optimal chemoselectivity. In this study, we demonstrate that inherent limitation can be strategically harnessed for asymmetric photoredox catalysis. By utilizing chiral catalyst to facilitate kinetic resolution between two enantiomers racemic radical intermediates, one enantiomer selectively undergoes desired transformation, while noncatalytic side reactions deplete other enantiomer. Consequently, an attractive three-component Minisci-type reaction involving bromides, homoallylic tertiary alcohols or amines, and azaarenes has been developed. This approach enables efficient assembly amines onto nonadjacent β-position azaarene-functionalized carbon stereogenic center with levels enantio- diastereoselectivity. Therefore, method not only allows direct utilization readily available feedstocks are challenging convert into prochiral via redox processes but also provides strategy synthesizing complex molecules multiple stereocenters.

Language: Английский

Citations

0
Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis DOI
Isaiah O. Betinol, Yutao Kuang,

Brian P. Mulley

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Chiral phosphoric acids (CPAs) have emerged as highly effective Brønsted acid catalysts in an expanding range of asymmetric transformations, often through novel multifunctional substrate activation modes. Versatile and broadly appealing, these benefit from modular tunable structures, compatibility with additives. Given the unique types noncovalent interactions (NCIs) that can be established between CPAs various reactants─such hydrogen bonding, aromatic interactions, van der Waals forces─it is unsurprising catalyst systems become a promising approach for accessing diverse chiral product outcomes. This review aims to provide in-depth exploration mechanisms by which impart stereoselectivity, positioning NCIs central feature connects broad spectrum catalytic reactions. Spanning literature 2004 2024, it covers nucleophilic additions, radical atroposelective bond formations, highlighting applicability CPA organocatalysis. Special emphasis placed on structural mechanistic features govern CPA-substrate well tools techniques developed enhance our understanding their behavior. In addition emphasizing details stereocontrolling elements individual reactions, we carefully structured this natural progression specifics broader, class-level perspective. Overall, findings underscore critical role catalysis significant contributions advancing synthesis.

Language: Английский

Citations

0
Chiral Magnesium(II)-Catalyzed Asymmetric Hydroalkylation of Imine-Containing Vinylazaarenes through Conjugate Addition DOI
Dong Ye, Mingyi Jiang, Lichao Ning

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 29, 2025

The synthesis of chiral azaarenes is great importance for pharmaceutical development. A direct and versatile approach to obtaining such compounds the functionalization imine-containing 2-vinylazaarenes. We have developed a N,N'-dioxide/Mg(II) Lewis acid catalytic system control nucleophilic β-cyclic or acyclic ketone amides/esters overcome strong background reaction, enabling highly efficient enantioselective hydroalkylation 2-vinylazaarenes via conjugate addition. As result, library bearing an all-carbon quaternary stereocenter can be obtained in high yields with good excellent ee values. DFT calculations indicate assistances hydrogen transfer, CH-π interaction between substrate ligand's amide group differentiation.

Language: Английский

Citations

0