Catalytic Asymmetric Diastereodivergent Synthesis of 2-Alkenylindoles Bearing both Axial and Central Chirality

Precision Chemistry, Journal Year: 2024, Volume and Issue: 2(5), P. 208 - 220

Published: April 23, 2024

The catalytic asymmetric diastereodivergent synthesis of axially chiral 2-alkenylindoles was established via phosphoric acid-catalyzed addition reactions C3-unsubstituted with

Language: Английский

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Dynamic Kinetic Reductive Grignard-Type Addition for the Construction of Axial and Central Chirality

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1147 - 1157

Published: Jan. 3, 2025

This study describes a photoredox/cobalt dual-catalyzed asymmetric Grignard-type addition reaction, enabling the synthesis of axially chiral hexatomic (six–six) N-heterobiaryls bearing extra secondary alcohol unit via an efficient dynamic kinetic transformation racemic N-heterobiaryl triflate substrates. The conversion facilitated both photoredox and classical reductive reaction conditions exhibits good functional group tolerance, broad substrate scope, satisfactory stereoselectivity. Furthermore, control experiments density theory calculations provide preliminary mechanistic insights.

Language: Английский

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Expedient Synthesis of Axially and Centrally Chiral Diaryl Ethers via Cobalt-Catalyzed Photoreductive Desymmetrization

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4638 - 4647

Published: March 12, 2024

Axially chiral diaryl ethers make up a unique class of atropisomers bearing restricted rotation about the C–O bond. Methods for expedient synthesis axially ether-based structures have been largely underdeveloped. Herein, we developed an efficient metal-catalyzed desymmetrization strategy to unveil formation and centrally dual in high diastereo- enantioselectivity. The protocol leverages cobalt-catalyzed photoreductive enantioselective couplings dialdehyde alkyne deliver stereogenicity, ether scaffold is equipped with useful synthetic handles including formyl, hydroxyl, allyl groups, as has demonstrated carboxylic acid potential ligand asymmetric catalysis.

Language: Английский

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Atroposelective Synthesis of N–N Axially Chiral Indoles and Pyrroles via NHC-Catalyzed Diastereoselective (3 + 3) Annulation Strategy

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6965 - 6972

Published: April 18, 2024

The synthesis of N–N axially chiral molecules in the enantiopure form has emerged as an interesting research topic primarily due to significance and intricacy synthesizing these molecules, especially bearing heterocyclic motifs. Herein, we disclose a method for introduction axial chirality along with point center via N-heterocyclic carbene (NHC)-catalyzed atroposelective dihydropyridinone-containing indoles pyrroles. reaction follows (3 + 3) annulation approach by interception indole/pyrrole-derived enamines α,β-unsaturated aldehydes under oxidative NHC catalysis proceeding acylazoliums. indoles/pyrroles were formed mild conditions broad scope high selectivity. In addition, preliminary DFT studies rotational barrier products performed.

Language: Английский

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Enantioselective synthesis of molecules with multiple stereogenic elements

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(22), P. 11165 - 11206

Published: Jan. 1, 2024

This review explores the fascinating world of molecules featuring multiple stereogenic elements, unraveling different strategies designed over years for their enantioselective synthesis.

Language: Английский

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Atroposelective Synthesis of Axially Chiral Diaryl Ethers by N-Heterocyclic-Carbene-Catalyzed Sequentially Desymmetric/Kinetic Resolution Process

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 4067 - 4073

Published: Feb. 23, 2024

We describe herein an N-heterocyclic-carbene-catalyzed atroposelective synthesis of axially chiral diaryl ethers. Through a sequentially enantioselective desymmetric process and kinetic resolution process, the products could be constructed in good yields with excellent enantiopurities. Both alcohols phenols were compatible this catalytic system. The carboxylic acids derived from esters proven to potential ligands for asymmetric synthesis, example, Rh(III)-catalyzed C–H functionalization.

Language: Английский

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A Comprehensive Review on the Enantiomeric Separation of Chiral Drugs Using Metal-Organic Frameworks

Chemosphere, Journal Year: 2024, Volume and Issue: 364, P. 143083 - 143083

Published: Aug. 16, 2024

Language: Английский

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Cobalt‐Catalyzed Enantioselective Alkenylation of Aldehydes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 31, 2024

Catalytic enantioselective alkenylation of aldehydes with easily accessible alkenyl halides promoted by a chiral cobalt complex derived from newly developed tridentate bisoxazolinephosphine is presented. Such processes represent an unprecedented reaction pathway for catalysis and general approach that enable rapid construction highly diversified enantioenriched allylic alcohols containing 1,1-, 1,2-disubstituted trisubstituted alkene as well axial stereogenicity in up to 99 % yield : 1 er without the need preformation alkenyl-metal reagents. DFT calculations revealed origin enantioselectivity.

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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Stereodivergent Protein Engineering of Fatty Acid Photodecarboxylase for Light‐Driven Kinetic Resolution of Sec‐Alcohol Oxalates

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 10, 2024

Stereodivergent engineering of one enzyme to create stereocomplementary variants for synthesizing optically pure molecules with tailor-made (R) or (S) configurations on an optional basis is highly desirable and challenging. This study aimed engineer fatty acid photodecarboxylase from Chlorella variabilis (CvFAP) using the focused rational iterative site-specific mutagenesis (FRISM) strategy obtain two excellent selectivity (both giving products up 99 % e.e.). These were used CvFAP-catalyzed light-driven kinetic resolution oxalates oxamic acids prepared corresponding sec-alcohols amines, providing a new biotransformation process preparing chiral amines. Molecular dynamics simulation, data transient spectra revealed source selectivity. represents first example amines catalyzed by pair CvFAPs.

Language: Английский

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