Catalytic atroposelective synthesis

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(5), P. 483 - 498

Published: April 30, 2024

Language: Английский

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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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Design and Catalytic Asymmetric Synthesis of Furan‐Indole Compounds Bearing both Axial and Central Chirality

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(8)

Published: Dec. 29, 2023

Abstract In the chemistry community, catalytic asymmetric synthesis of furan‐based compounds bearing both axial and central chirality has proven to be a significant but challenging issue owing importance difficulty in constructing such frameworks. this work, we have realized first five‐five‐membered via organocatalytic (2+4) annulation achiral furan‐indoles with 2,3‐indolyldimethanols uncommon regioselectivity. By strategy, furan‐indole were synthesized high yields excellent regio‐, diastereo‐, enantioselectivities. Moreover, theoretical calculations conducted provide an in‐depth understanding reaction pathway, activation mode, origin selectivity.

Language: Английский

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Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(18), P. 12134 - 12141

Published: Aug. 30, 2023

A highly enantio- and diastereoselective dynamic kinetic resolution (DKR) of configurationally labile 3-aryl indole-2-carbaldehydes is described. The DKR proceeds via a Rh-catalyzed intermolecular asymmetric reductive aldol reaction with acrylate esters, simultaneous generation three stereogenic elements. strategy relies on the labilization axis that takes place thanks to transient Lewis acid-base interaction (LABI) between formyl group thioether moiety strategically located at ortho' position. atropisomeric indole products present high degree functionalization can be further converted series axially chiral derivatives, thereby expanding their potential application in drug discovery catalysis.

Language: Английский

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Atroposelective catalysis

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 497 - 517

Published: June 18, 2024

Language: Английский

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Enantioselective Rhodium‐Catalyzed C−H Arylation Enables Direct Synthesis of Atropisomeric Phosphines

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(8)

Published: Jan. 6, 2024

Atropisomeric phosphines hold considerable significance in asymmetric catalysis, yet their synthesis presents a formidable challenge owing to intricate multistep procedures. In this context, groundbreaking methodology has been presented for preparation. This innovative approach entails an atroposelective rhodium-catalyzed C-H activation employing aryl and heteroaryl halides, chelated by P(III) center. The essence of strategy lies its ability directly construct chiral phosphine ligands single step, thereby exhibiting exceptional efficiency terms atom redox economy. Illustrative examples serve demonstrate the immense potential situ-formed catalysis. Mechanistic experiments have further provided invaluable insights into transformation.

Language: Английский

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Iron-catalyzed stereoselective C–H alkylation for simultaneous construction of C–N axial and C-central chirality

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

Published: April 25, 2024

Abstract The assembly of chiral molecules with multiple stereogenic elements is challenging, and, despite indisputable advances, largely limited to toxic, cost-intensive and precious metal catalysts. In sharp contrast, we herein disclose a versatile C–H alkylation using non-toxic, low-cost iron catalyst for the synthesis substituted indoles two elements. key achieving excellent diastereo- enantioselectivity was substitution on N -heterocyclic carbene ligand providing steric hindrance extra represented by noncovalent interaction concomitant generation C–N axial chirality C -stereogenic center. Experimental computational mechanistic studies have unraveled origin catalytic efficacy stereoselectivity.

Language: Английский

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Silver-Catalyzed Direct Nucleophilic Cyclization: Enantioselective De Novo Synthesis of C–C Axially Chiral 2-Arylindoles

Organic Letters, Journal Year: 2023, Volume and Issue: 25(3), P. 522 - 527

Published: Jan. 18, 2023

Atropisomeric indoles widely exist in natural products, pharmaceuticals, functional materials, and catalysts for their featured biological activities, photoelectric properties, catalytic while facile de novo construction of this motif remains underexplored. Herein, we report a chiral silver phosphate-catalyzed direct 5-endo-dig nucleophilic cyclization 2-alkynylanilins under mild conditions, affording various C-C axially 2-arylindoles high to excellent yields enantioselectivities. Control experiments implied the cooperative catalysis AgOAc phosphoric acid, wherein former accelerated desired transformation latter improved enantioselectivity. In addition, as first example silver-catalyzed enantioselective synthesis indole skeletons, synthetic applications products' thermal stability have been investigated.

Language: Английский

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Pd-Catalyzed Asymmetric Amination of Enamines: Expedient Synthesis of Structurally Diverse N–C Atropisomers

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(11), P. 7680 - 7690

Published: May 23, 2023

The transition-metal-catalyzed cross-coupling of enamines is an attractive method for producing compounds with N–C chiral axis; however, it faces considerable challenges that remain unresolved. Herein, a palladium-catalyzed amination was developed to construct structurally diverse five–six biaryl and six–six nonbiaryl atropisomers. reaction mechanism explained using density functional theory calculations, which showed the involved Curtin–Hammett control. rotation occurred along coordinate until enantio-determining three-centered reductive elimination transition structure established stereochemistry. highly because its broad substrate scope, high stereoselectivity, simple catalytic system, good group tolerance, dynamic kinetic resolution.

Language: Английский

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Organocatalytic Nazarov-type cyclization of 3-alkynyl-2-indolylmethanols: construction of axially chiral cyclopenta[b]indole scaffolds

Chemical Synthesis, Journal Year: 2023, Volume and Issue: 3(1), P. 6 - 6

Published: Jan. 1, 2023

In recent years, it has become an urgent task to design new types of indole-based platform molecules for Nazarov-type cyclizations and develop organocatalytic synthesizing indole derivatives. To fulfill this task, in work, by changing the alkynyl terminal substituent from t-Bu aryl group, reactivity 3-alkynyl-2-indolylmethanols is modulated serve as competent substrates Brønsted acid-catalyzed cyclization. Based on reactivity, first cyclization aryl-substituted with 2-naphthols accomplished, leading efficient construction a class axially chiral 3, 4-dihydrocyclopenta[b]indole scaffolds. This preliminary investigation asymmetric provides optional strategy atroposelective cyclopenta[b]indole addition, preparation optical purity established through resolution, which could complementary method catalytic approaches.

Language: Английский

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