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 DOI
Jijie Wang, Lei Tang, Yuanjiu Xiao

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(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

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 DOI
Jijie Wang, Lei Tang, Yuanjiu Xiao

et al.

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

Citations

40
Catalytic asymmetric (3 + 3) cycloaddition between different 2-indolylmethanols DOI
Tianzhen Li, Sijia Liu, Shufang Wu

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(8), P. 2629 - 2636

Published: June 26, 2024

Language: Английский

Citations

26
Catalytic atroposelective synthesis of indolyl quinazolinones bearing N–N/C–C diaxes DOI

Ning‐Yi Wang,

Shuo Gao,

Zhiwei Shu

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Language: Английский

Citations

6
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

33
Catalytic Asymmetric Diastereodivergent Synthesis of 2-Alkenylindoles Bearing both Axial and Central Chirality DOI Creative Commons
Shuang Yang,

Jia-Bo Huang,

Dahua Wang

et al.

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

Citations

17
Enantioselective Tsuji‐Trost α‐Fluoroallylation of Amino Acid Esters with Gem‐Difluorinated Cyclopropanes DOI
Zheng Su,

Binhong Tan,

Hui He

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: Feb. 27, 2024

A novel enantioselective Tsuji-Trost-type cross coupling reaction between gem-difluorinated cyclopropanes and N-unprotected amino acid esters enabled by synergistic Pd/Ni/chiral aldehyde catalysis is presented herein. This transformation streamlined the diversity-oriented synthesis (DOS) of optically active α-quaternary α-amino bearing a linear 2-fluoroallylic motif, which served as an appealing platform for construction other valuable enantioenriched compounds. The key intermediates were confirmed HRMS detection, while DFT calculations revealed that excellent enantioselectivity was attributed to stabilizing non-covalent interactions Pd(II)-π-fluoroallyl species Ni(II)-Schiff base complex.

Language: Английский

Citations

12
Synthesis of Alkene Atropisomers with Multiple Stereogenic Elements via Catalytic Asymmetric Rearrangement of 3‐Indolylmethanols DOI
Ping Wu,

Wen‐Tao Zhang,

Jixiang Yang

et al.

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

Citations

10
Atroposelective Synthesis of Planar‐Chiral Indoles via Carbene Catalyzed Macrocyclization DOI
Gongming Yang, Yi He, Tianyi Wang

et al.

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

Published: Nov. 28, 2023

Abstract Indole‐based planar‐chiral macrocycles are widely found in natural products and bioactive molecules. However, sharp contrast to the preparation of indole‐based axially chiral structures, enantioselective catalysis is still a formidable task so far. Here we report an N ‐heterocyclic carbene (NHC)‐catalyzed intramolecular atroposelective macrocyclization 3‐carboxaldehyde indole/pyrroles, featuring with broad substrate scope good functional group tolerance, allowing for rapid access diverse indole/pyrrole‐based various tether‐lengths (10–16 members) yields excellent enantioselectivities. Importantly, macrocyclic structures both planar axial chirality were directly efficiently obtained through this protocol enantioselectivities diastereoselectivities. In addition, these synthesized offer many possibilities chemists develop new catalysts or ligands, as well reactions.

Language: Английский

Citations

21
Design of rigid chiral bipyridine-2NO tetradentate ligands: application in asymmetric catalysis DOI
Yuheng Wang, Pan Hu, Xirui Wang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(5), P. 1314 - 1321

Published: Jan. 1, 2024

A new class of chiral bipyridine-2NO ligands, which incorporate the advantages both bipyridine skeleton and pyrroloimidazolone-based N -oxide moiety, was developed.

Language: Английский

Citations

9
Catalyst-controlled directing group translocation in the site selective C–H functionalization of 3-carboxamide indoles and metallocarbenes DOI Creative Commons

Kuang Gu,

Mary P. Hall,

Zachary D. Tucker

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 2, 2025

Complementary methods toward the selective functionalization of indole and oxindole frameworks employing an alternative strategy in heteroaryl C–H functionalizations are presented herein. This work focuses on a catalyst-controlled, site activation/functionalization 3-acyl indoles, wherein amide serves as robust versatile directing group capable undergoing concomitant 1,2-acyl translocation/C–H presence RhI/AgI co-catalysts to provide cross-coupled adducts high yields. In contrast, use IrIII/AgI catalysts subverted migration afford corresponding C2-functionalized products good excellent A notable feature catalyst systems was exceptional level selectivity observed which functionalized indoles were obtained exclusively. Mechanistic experiments indicate concerted step metallation occurring through electrophilic aromatic substitution process. Here, authors present divergent, transition metal catalyst-controlled 3-carboxamide indoles. One set conditions enables 2-position, while other translocation carboxamide at 3-position.

Language: Английский

Citations

1