Organocatalytic Nazarov-type cyclization of 3-alkynyl-2-indolylmethanols: construction of axially chiral cyclopenta[b]indole scaffolds DOI Open Access
Ping Wu, Xinyu Yan,

Song Jiang

et al.

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

Ruthenium(II)/Imidazolidine Carboxylic Acid‐Catalyzed C−H Alkylation for Central and Axial Double Enantio‐Induction DOI Creative Commons
Yanjun Li,

Yan‐Cheng Liou,

João C. A. Oliveira

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(47)

Published: Sept. 15, 2022

Enantioselective C-H activation has surfaced as a transformative toolbox for the efficient assembly of chiral molecules. However, despite major advances in rhodium and palladium catalysis, ruthenium(II)-catalyzed enantioselective thus far largely proven elusive. In contrast, we herein report on highly regio-, diastereo- alkylation. The key to success was represented by identification novel C2-symmetric imidazolidine carboxylic acids (CICAs), which are easily accessible one-pot fashion, effective ligands. This ruthenium/CICA system enabled installation central axial chirality, featured excellent branched linear ratios with generally >20 : 1 dr up 98 2 er. Mechanistic studies experiment computation were carried out understand catalyst mode action.

Language: Английский

Citations

56
Thioether-enabled palladium-catalyzed atroposelective C–H olefination for N–C and C–C axial chirality DOI Creative Commons
Yanjun Li,

Yan‐Cheng Liou,

Xinran Chen

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(14), P. 4088 - 4094

Published: Jan. 1, 2022

Thioethers allowed for highly atroposelective C-H olefinations by a palladium/chiral phosphoric acid catalytic system under ambient air. Both N-C and C-C axial chiral (hetero)biaryls were successfully constructed, leading to broad range of axially

Language: Английский

Citations

47
Design and Catalytic Asymmetric Synthesis of Furan‐Indole Compounds Bearing both Axial and Central Chirality DOI
Jing‐Yi Wang,

Cong‐Hui Gao,

Cheng Ma

et al.

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

Citations

32
Atroposelective catalysis DOI

Tanno A. Schmidt,

Valeriia Hutskalova,

Christof Sparr

et al.

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

Published: June 18, 2024

Language: Английский

Citations

16
Enantioselective synthesis of molecules with multiple stereogenic elements DOI Creative Commons
Arthur Gaucherand, Expédite Yen‐Pon,

Antoine Domain

et al.

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

Citations

15
Asymmetric Synthesis of Axially Chiral Naphthyl-C3-indoles via a Palladium-Catalyzed Cacchi Reaction DOI

Cong-Shuai Wang,

Liang Wei, Cong Fu

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(19), P. 7401 - 7406

Published: Sept. 17, 2021

Atropoisomeric biaryl motifs are widely found in natural products and bioactive compounds as well chiral catalysts ligands. Various efficient approaches have been disclosed for the construction of six–six skeletons. In contrast, enantioselective synthesis axially arylindoles through strategy de novo construction, other than asymmetric functionalization indoles, remain a challenging task. Herein we report an Pd(0)/(S)-Segphos-catalyzed atroposelective Cacchi reaction 2-alkynylanilines with sterically congested naphthyl halides, which afforded array naphthyl-C3-indoles high yields good to excellent atroposelectivities. The addition water modulation manipulation procedure by premixing palladium complex halide were keys success. conformational stability obtained naphthyl-C3-indole containing synthetically more-valuable free NH moiety is revealed kinetic experiments.

Language: Английский

Citations

48
Recent Advances in Catalytic Atroposelective Construction of Pentatomic Heterobiaryl Scaffolds DOI
Xiao‐Long He, Cheng Wang,

You‐Wu Wen

et al.

ChemCatChem, Journal Year: 2021, Volume and Issue: 13(16), P. 3547 - 3564

Published: June 7, 2021

Abstract Pentatomic heterobiaryl performs as a key structural motif in various natural products and bioactive compounds. With the rapid growth of asymmetric catalysis, five‐membered heterobiaryl‐based catalysts ligands have emerged an efficient complementary toolbox for catalysis. Therefore, development enantioselective construction such pentatomic atropisomers has received significant attention recent decade. Various catalytic strategies been established, including central to axial chirality conversion, direct generation heteroaryl, assembly aryl‐heteroaryls, functionalization racemic or prochiral biaryls, transfer from atropisomeric alkenes. Hundreds unprecedented proliferated. Importantly, few promising axially chiral obtained prepared heterobiaryls after simple transformations. Hence, advances through catalysis are summarized this review, involving their scope, mechanism, transformations, applications.

Language: Английский

Citations

45
SCpRh(III)-Catalyzed Enantioselective Synthesis of Atropisomers by C2-Arylation of Indoles with 1-Diazonaphthoquinones DOI

Si‐Yong Yin,

Chongqing Pan, Wenwen Zhang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(20), P. 3620 - 3625

Published: May 16, 2022

The Rh(III)-catalyzed highly enantioselective C2-arylation of indole derivatives with 1-diazonaphthoquinones is reported. In the presence 2.5 mol % SCpRh complex and 20 AgNO3, reactions indoles proceeded smoothly, affording a wide range C2-arylated atropisomers in good yields enantioselectivity (≤96% yield, ≤97% ee) under mild conditions. method displays broad substrate scope functional group tolerance.

Language: Английский

Citations

38
Design and Organocatalytic Asymmetric Synthesis of Indolyl-Pyrroloindoles Bearing Both Axial and Central Chirality DOI
Haiqing Wang, Shufang Wu, Junru Yang

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 88(12), P. 7684 - 7702

Published: Nov. 23, 2022

An axially chiral indolyl-pyrroloindole scaffold, a new member of indole-based scaffolds, has been designed, and the catalytic asymmetric construction this scaffold established by strategy organocatalytic (2 + 3) cycloaddition 3,3'-bisindoles with isoindolinone-based propargylic alcohols. By approach, series derivatives bearing both axial chirality central were synthesized in high yields excellent diastereo- enantioselectivities (up to 95% yield, 91:9 dr, 99% ee). This reaction not only realizes first n) as 1,2-dinucleophiles but also provides for atroposelective scaffolds five-five-membered rings, thus solving challenges constructing class scaffolds.

Language: Английский

Citations

37
Access to axially chiral aryl 1,3-dienes by transient group directed asymmetric C–H alkenylations DOI

Cong Shen,

Yuhang Zhu,

Wenzhou Shen

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(8), P. 2109 - 2115

Published: Jan. 1, 2022

An enantioselective olefinic C–H alkenylation using transient group was disclosed to afford axially chiral aryl 1,3-dienes in up 99% yields and >99% ee. The derived carboxylic acid efficient ligand asymmetric alkylation.

Language: Английский

Citations

33