Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Nov. 2, 2023

With the rapid development of asymmetric catalysis, demand for enantioselective synthesis complex and diverse molecules with different chiral elements is increasing. Owing to unique features atropisomerism, catalytic atropisomers has attracted a considerable interest from chemical science community. In particular, introducing additional elements, such as carbon centered chirality, heteroatomic planar helical into provides an opportunity incorporate new properties axially compounds, thus expanding potential applications atropisomers. Thus, it important perform transformations synthesize bearing multiple elements. spite challenges in transformations, recent years, chemists have devised powerful strategies under organocatalysis or metal synthesizing wide range enantioenriched Therefore, become emerging field. This review summarizes progress this field indicates challenges, thereby promoting horizon.

Language: Английский

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Switching between the [2π+2σ] and Hetero‐[4π+2σ] Cycloaddition Reactivity of Bicyclobutanes with Lewis Acid Catalysts Enables the Synthesis of Spirocycles and Bridged Heterocycles

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: May 11, 2024

Abstract The exploration of the complex chemical diversity bicyclo[n.1.1]alkanes and their use as benzene bioisosteres has garnered significant attention over past two decades. Regiodivergent syntheses thiabicyclo[4.1.1]octanes (S‐BCOs) highly substituted bicyclo[2.1.1]hexanes (BCHs) using a Lewis acid‐catalyzed formal cycloaddition bicyclobutanes (BCBs) 3‐benzylideneindoline‐2‐thione derivatives have been established. first hetero‐(4+3) BCBs, catalyzed by Zn(OTf) 2 , was achieved with broad substrate scope under mild conditions. In contrast, less electrophilic BCB ester undergoes Sc(OTf) 3 ‐catalyzed [2π+2σ] reaction 1,1,2‐trisubstituted alkenes, yielding BCHs spirocyclic quaternary carbon center. Control experiments preliminary theoretical calculations suggest that diastereoselective product formation may involve concerted between zwitterionic intermediate E ‐1,1,2‐trisubstituted alkenes. Additionally, nucleophilic ring‐opening mechanism.

Language: Английский

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Advances in Catalytic Asymmetric Reactions Involving o-Hydroxybenzyl Alcohols

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(3), P. 974 - 974

Published: Jan. 1, 2023

a 江苏师范大学化学与材料科学学院 江苏徐州 221116

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Photocatalytic Sulfonylation: Innovations and Applications

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 14, 2024

Photosynthesis, converting sustainable solar energy into chemical energy, has emerged as a promising craft to achieve diverse organic transformations due its mild reaction conditions, sustainability, and high efficiency. The synthesis of sulfonated compounds drawn significant attention in the pharmaceuticals, agrochemicals, materials industries unique structure electronic properties sulfonyl groups. Over past decades, many photocatalytic sulfonylation reactions have been developed. In this review, recent advances photocatalyzed reviewed since 2020, with primary focus on discussing design mechanism.

Language: Английский

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Stereoselective synthesis of substituted 1,3-dienes from propargylic esters: electrophilic-metal or redox catalysis?

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(5), P. 1384 - 1396

Published: March 22, 2024

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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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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Lewis Acid-Enabled Chemodivergent Cycloadditions of Donor–Acceptor Cyclopropanes with Indoline-2-Thiones

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 20, 2025

Lewis acid-enabled reactions of donor-acceptor cyclopropanes (DACs) with indoline-2-thiones are reported. The reaction exhibits tunable annulation depending on the acid and substituent at N1 indoline-2-thiones. With AlCl3 as 1-isopropylindoline-2-thiones reactants, a direct ring opening DACs, followed by intramolecular nucleophilic addition/dehydration takes place leading to formation dihydro-2H-thiepino[2,3-b]indoles in moderate good yields. Using Yb(OTf)3 promoter 1-unsubstituted (3 + 2) cycloaddition DACs accompanied sulfur rearrangement give 3-indolyl-4,5-dihydrothiophenes In addition, synthetic transformation 3-indolyl-4,5-dihydrothiophene sulfone indole-based axially chiral scaffolds further extends utility structural complexity.

Language: Английский

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Asymmetric Trapping of Siloxyketenes In Situ Generated from [1,3]-Silyl Migration of α-Ketoacylsilanes: A Visible-Light-Driven Palladium-Catalyzed [4 + 2] Cycloaddition

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5796 - 5805

Published: March 25, 2025

The transition metal-catalyzed asymmetric [n + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable precursors. Herein, we report visible-light-driven, palladium-catalyzed [4 vinyl benzoxazinanones siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives satisfactory diastereo- and enantioselectivities. transient generation siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for success present cycloaddition. 13C-labeling experiments reveal pathway involving [1,3]-silyl migration process. side arm effects BOX ligand silyl steric hindrance α-ketoacylsilanes play crucial roles in stereoselectivity control, theoretical calculations provide insights into stereochemical outcome reaction.

Language: Английский

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Advances in Catalytic Asymmetric Reactions Involving o-Hydroxyphenyl Substituted p-Quinone Methides^★

Acta Chimica Sinica, Journal Year: 2023, Volume and Issue: 81(7), P. 793 - 793

Published: Jan. 1, 2023

o-Hydroxyphenyl substituted p-quinone methides (p-QMs) belong to a class of p-QMs with unique advantages.They not only maintain the high reactivity p-QMs, but also have more reactive and activation sites owing introduction hydroxyl group.Therefore, o-hydroxyphenyl wide applications in synthetic medicinal chemistry.The catalytic asymmetric 1,6-conjugate addition [4＋n] cycloaddition developed very rapidly recent years, which become efficient strategies for synthesis chiral oxygen-containing heterocycles arylmethanes potential bioactivity.This review summarizes reactions involving points out remaining challenges this research area, will open new window design type their involved reactions.

Language: Английский

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