Enantioselective Access to Triaryl-2-pyrones with Monoaxial or Contiguous C–C Diaxes via Oxidative NHC Catalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2565 - 2575

Published: Feb. 6, 2023

We present herein an unprecedented stereoselective synthesis of triaryl-2-pyrones with monoaxial or contiguous diaxes from readily available starting materials. This N-heterocyclic carbene catalysis method adopts atroposelective annulation 2-aryketones ynals under oxidative conditions. The includes the construction one two axes in a single operation, achieves step economy, and affords axially chiral moderate to good yields, high excellent enantioselectivities. DFT calculations relative energies stereoisomers rotational barriers were performed.

Language: Английский

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Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

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

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Atroposelective Construction of Carbon–Boron Axial Chirality through Rh-Catalyzed [2 + 2 + 2] Cycloaddition

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5064 - 5076

Published: March 20, 2024

Axially chiral compounds have widespread applications in many fields. While significant progress has been made for the asymmetric synthesis of atropisomers consisting C–C bonds, an efficient approach construction C–B is still lacking. Herein, we report a practical method atroposelective axially arylboron through Rh-catalyzed [2 + 2 2] cycloaddition. The reaction exhibits broad substrate scope and good functional group tolerance, thus providing protocol to access variety high yields enantiocontrol. utility these adequately demonstrated by versatile transformations into highly valuable such as phosphine ligands fluorescent molecules. Mechanistic experiments DFT calculations provided insights mechanism well origin

Language: Английский

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Synthesis of Alkene Atropisomers with Multiple Stereogenic Elements via Catalytic Asymmetric Rearrangement of 3‐Indolylmethanols

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 23, 2024

Abstract Catalytic enantioselective preparation of alkene atropisomers with multiple stereogenic elements and discovery their applications have become significant but challenging issues in the scientific community due to unique structures this class atropisomers. We herein report first catalytic atroposelective cyclopentenyl[ b ]indoles, a new kind atropisomers, point axial chirality via an unusual rearrangement reaction 3‐indolylmethanols under asymmetric organocatalysis. Notably, novel type promising developing chiral ligands or organocatalysts, discovering antitumor drug candidates fluorescence imaging materials. Moreover, theoretical calculations elucidated possible mechanism non‐covalent interactions control enantioselectivity. This approach offers synthetic strategy for elements, represents 3‐indolylmethanols, which will advance chemistry indole chemistry.

Language: Английский

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Copper-Catalyzed Intermolecular [2 + 2 + 2] Annulation of Diynes with Alkynes: Construction of Carbazoles

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

Published: Jan. 9, 2025

Transition-metal-catalyzed [2 + 2 2] annulation of alkynes is an efficient pathway for the synthesis aromatic compounds. However, most established methods require noble metal catalysts. Herein, we report a copper-catalyzed intermolecular diynes with through vinyl cation intermediates, enabling atom-economical preparation biologically important carbazole skeletons. The reaction shows good regioselectivity in aryl(alkyl)alkynes. Moreover, preliminary results have also been obtained related catalytic atroposelective transformation. This represents rare example non-noble-metal-catalyzed ynamides pathway.

Language: Английский

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Enantioselective [2+2+2] Cycloaddition of Internal Alkynes to Access Axially Chiral Biaryl Hexasubstituted Benzene

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2939 - 2949

Published: Feb. 4, 2025

Language: Английский

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Organocatalytic Atroposelective Hydroselenation of Alkynes To Access Axially Chiral Vinyl Selenides

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4051 - 4060

Published: Feb. 20, 2025

Language: Английский

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Atroposelective Synthesis of Axially Chiral Styrenes Connecting an Axially Chiral Naphthyl-indole Moiety Using Chiral Phosphoric Acid Catalysis

Organic Letters, Journal Year: 2023, Volume and Issue: 25(12), P. 2068 - 2072

Published: March 20, 2023

The organocatalytic asymmetric reactions of C2-unsubstituted racemic naphthyl-indoles with orthoalkynylnaphthols were employed to synthesize axially chiral styrenes connected an naphthyl-indole unit. Utilizing phosphoric acid as the catalyst, these prepared in good yields (up 96%) and excellent stereoselectivity >99.9% ee, >20:1 dr, >99:1 E/Z) mild conditions. Moreover, further synthetic transformations achieved high stereocontrol.

Language: Английский

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Room Temperature Fluoranthene Synthesis through Cationic Rh(I)/H₈-BINAP-Catalyzed [2 + 2 + 2] Cycloaddition: Unexpected Acceleration due to Noncovalent Interactions

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(3), P. 1604 - 1613

Published: Jan. 12, 2023

The fluoranthene skeleton is a structure often found in natural products and fluorescent materials, thus developing an operationally simple method for diversity-oriented synthesis important research topic organic synthesis. However, existing synthetic methods require harsh reaction conditions or limited substrate applicability both. Here, we report the room temperature of substituted fluoranthenes azafluoranthenes through cationic Rh(I)/H8-BINAP complex-catalyzed [2 + 2 2] cycloaddition using 1,8-dialkynylnaphthalenes. DFT calculations reveal that H8-BINAP ligand stabilizes intermediates, allowing reaction. Among substrates examined, 1,8-bis(phenylethynyl)naphthalene diarylacetylenes show high reactivity, contrary to reactivity predicted by their steric bulkiness. Theoretical experimental mechanistic studies have demonstrated noncovalent interactions phenyl groups on both accelerate present sterically demanding reactions stabilizing transition states rather than inducing repulsions.

Language: Английский

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Asymmetric Allylic Substitution‐Isomerization for the Modular Synthesis of Axially Chiral N‐Vinylquinazolinones

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

Published: Aug. 16, 2023

Abstract Axially chiral N ‐substituted quinazolinones are important bioactive molecules, which presented in many synthetic drugs. However, most strategies toward their atroposelective synthesis mainly limited to the axially arylquinazolinone frameworks. The development of modular methods access diverse quinazolinone‐based atropisomers remains scarce and challenging. Herein, we report regio‐ ‐vinylquinazolinones via strategy asymmetric allylic substitution‐isomerization. catalysis system utilized both transition‐metal organocatalysis efficiently afford trisubstituted tetrasubstituted ‐vinylquinazolinone atropisomers, respectively. With meticulous design β‐substituted substrates, Z ‐ E ‐tetrasubstituted were obtained good yields high enantioselectivities.

Language: Английский

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