Unified Enantioselective Allylations and Vinylogous Reactions Enabled by Visible Light-Driven Chiral Lewis Acid Catalysis DOI
Fuyuan Li, Fang‐Hua Liu, Xiaowei Zhao

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 16479 - 16487

Published: Oct. 23, 2024

In contemporary organic synthesis, chemists actively pursue a diverse range of substrates that can be efficiently catalyzed within an integrated system, playing crucial role in advancing the pharmaceutical industry. However, due to influence substituents on reactivity and selectivity, it poses challenging dilemma explore different strategies for activating with distinct functional groups. Herein, we have developed important visible light-driven chiral Lewis acid catalysis platform which facilitates unified allylations vinylogous reactions various allyl bromides isatins highly enantio- diastereoselective construction valuable 3-allyl-3-hydroxy oxindoles. The success this approach lies utilizing radical pathway intermediate formation stereocenter generation. Moreover, activation capability acids provides opportunity achieve sufficient enantiocontrol enhance regioselectivity. robustness method is demonstrated by its application precise radical-based propargylation using readily accessible propargyl bromides.

Language: Английский

Asymmetric Cross-Coupling of Aldehydes with Diverse Carbonyl or Iminyl Compounds by Photoredox-Mediated Cobalt Catalysis DOI

Zhiyong Chi,

Jia-Bin Liao,

Xiuliang Cheng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10857 - 10867

Published: April 8, 2024

The asymmetric cross-coupling of unsaturated bonds, hampered by their comparable polarity and reactivity, as well the scarcity efficient catalytic systems capable diastereo- enantiocontrol, presents a significant hurdle in organic synthesis. In this study, we introduce highly adaptable photochemical cobalt catalysis framework that facilitates chemo- stereoselective reductive cross-couplings between common aldehydes with broad array carbonyl iminyl compounds, including N-acylhydrazones, aryl ketones, aldehydes, α-keto esters. Our methodology hinges on synergistic mechanism driven photoredox-induced single-electron reduction subsequent radical–radical coupling, all precisely guided chiral catalyst. Various optically enriched β-amino alcohols unsymmetrical 1,2-diol derivatives (80 examples) have been synthesized good yields (up to 90% yield) high stereoselectivities >20:1 dr, 99% ee). Of particular note, approach accomplishes unattainable transformations disparate partners without reliance any external photosensitizer, thereby further emphasizing its versatility cost-efficiency.

Language: Английский

Citations

17
Catalytic Asymmetric Dearomative [2 + 2] Photocycloaddition/Ring-Expansion Sequence of Indoles with Diversified Alkenes DOI
Liuzhen Hou, Longqing Yang,

Gaofei Yang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23457 - 23466

Published: July 12, 2024

Developing novel strategies for catalytic asymmetric dearomatization (CADA) reactions is highly valuable. Visible light-mediated photocatalysis demonstrated to be a powerful tool activate aromatic compounds further synthetic transformations. Herein, dearomative [2 + 2] photocycloaddition/ring-expansion sequence of indoles with simple alkenes was reported, providing facile access enantioenriched cyclopenta[

Language: Английский

Citations

10
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
Iron‐Catalyzed Asymmetric α‐Alkylation of 2‐Acylimidazoles via Dehydrogenative Radical Cross‐Coupling with Alkanes DOI

Nian Xu,

Maoping Pu, Yu Han

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 21, 2023

The direct α-alkylation of acyclic carbonyls with nonactivated hydrocarbons through C(sp3 )-H functionalization is both extremely promising and notably challenging, especially when attempting to achieve enantioselectivity using iron-based catalysts. We have identified a robust chiral iron complex for the oxidative cross-coupling 2-acylimidazoles benzylic allylic hydrocarbons, as well alkanes. readily available tunable N,N'-dioxide catalysts in connection oxidants exhibit precise asymmetric induction (up 99 % ee) good compatibility moderate yields 88 yield). This protocol provides an elegant straightforward access optically active carbonyl derivatives starting from simple alkanes without prefunctionalization. Density functional theory (DFT) calculations control experiments were made gain insight into nature C-C bond formation origin enantioselectivity. propose radical-radical process enabled by immediate interconversion between ferric species ferrous species.

Language: Английский

Citations

14
Applications of Organosilanes in Visible Light‐induced Catalytic Asymmetric Reactions DOI
Liuzhen Hou, Weidi Cao, Xiaoming Feng

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: March 27, 2024

Abstract Over the past decades, visible light‐mediated photocatalysis has found a mainstream of applications in synthetic chemistry. Organosilanes have been proven to be useful class electron donors generate highly active radical species via photoinduced single transfer oxidation/fragmentation sequence, which may undergo follow‐up coupling or addition process. This minireview highlights comprehensive advances organosilanes photoredox catalyzed asymmetric organic synthesis, with particular emphasis placed on reaction mechanisms. We hope that this review will inspire further design and development new reactions such readily accessible reagents.

Language: Английский

Citations

4
Visible-light-driven asymmetric aldol reaction of ketones and glycinates via synergistic Lewis acid/photoredox catalysis DOI Creative Commons
Jiuqi Tan, Longqing Yang,

Hanyu Su

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(39), P. 16050 - 16058

Published: Jan. 1, 2024

We have synthesized β-diaryl-β-hydroxyl-α-amino acid derivatives through radical addition-type aldol reaction, which was confirmed by spectroscopic experiments, control and DFT calculations.

Language: Английский

Citations

4
Catalytic Asymmetric Synthesis of β-Amino α-Tertiary Alcohol through Borrowing Hydrogen Amination DOI
Shahida Perveen, Tariq Ali, Talat S. Rahman

et al.

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

Published: March 6, 2025

The first enantioconvergent transition-metal-catalyzed amination of racemic α-tertiary 1,2-diols providing access to vicinal β-amino alcohols is disclosed. iridium-catalyzed reaction proceeds through a chiral phosphoric acid-mediated borrowing hydrogen pathway with excellent yields and enantioselectivities for range amine nucleophiles 1,2-diols. An array were obtained high (50 examples up 91% yield 99% ee). These important amino alcohol products can be easily converted into ligands bioactive skeletons. Mechanistic investigations proposed dynamic kinetic resolution involving imine formation then reduction as the enantiodetermining step.

Language: Английский

Citations

0
Reduction of C=X to CH–XH by Dissolving Metals and Related Methods DOI
Nina Schützenmeister, Jasmin Janneschütz,

Justus Lackner

et al.

Elsevier eBooks, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

Citations

0
Enantioselective Hydroaminoalkylation of Azaaryl Ketones through Asymmetric Photoredox Catalysis DOI

Xiangbin Bai,

Jialu Yao,

Wenxian Li

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 5037 - 5042

Published: June 5, 2024

An enantioselective hydroaminoalkylation of azaaryl ketones under a transition-metal-free asymmetric photoredox catalysis platform is reported. A series valuable azaarene-functionalized 1,2-amino alcohols featuring attractive quaternary carbon stereocenters have been synthesized in high yields with good to excellent enantioselectivities. The viability readily accessible N-aryl glycines as reaction partners facilitates the conjugate modification these products into important derivatives, thereby enhancing synthetic utility current approach.

Language: Английский

Citations

3
Aza-[4 + 2]-cycloaddition of benzocyclobutenones into isoquinolinone derivatives enabled by photoinduced regio-specific C–C bond cleavage DOI Creative Commons
Liangkun Yang, Shiyang Li,

Lichao Ning

et al.

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

Published: Dec. 30, 2024

The activation of C-C bond benzocyclobutenones under mild reaction conditions remains a challenge. We herein report photoinduced catalyst-free regio-specific C1-C8 cleavage benzocyclobutenones, enabling the generation versatile ortho-quinoid ketene methides for aza-[4 + 2]-cycloaddition with imines, which offers facile route to isoquinolinone derivatives, including seven family members protoberberine alkaloids, gusanlung A, B, D, 8-oxotetrahydroplamatine, tetrahydrothalifendine, tetrahydropalmatine, and xylopinine. Furthermore, catalytic enantioselective version this strategy is also realized by merging synergistic photocatalysis chiral Lewis acid catalysis. Mechanistic studies provide compelling evidence rationalize photoisomerization/cycloaddition cascade process.

Language: Английский

Citations

2