Asymmetric one-carbon ring expansion of diverse N-heterocycles via copper-catalyzed diyne cyclization DOI Creative Commons

Fu-Shuai Li,

Xiuyuan Zou,

Tian-Qi Hu

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(41)

Published: Oct. 9, 2024

One-carbon ring expansion reaction of N-heterocycles has gained particular attention in the past decade because this method allows for conversion readily available into potentially useful complex ring-expanded N-heterocycles, which are inaccessible by traditional methods. However, catalytic asymmetric variant been rarely reported to date. Herein, we disclose an enantioselective one-carbon through chiral copper-catalyzed diyne cyclization, leading practical, atom-economic and divergent assembly array valuable bearing a quaternary stereocenter generally good excellent yields with enantioselectivities (up >99% ee). This protocol represents first example based on alkynes.

Language: Английский

Copper‐Catalyzed Enantioselective Doyle–Kirmse Reaction of Azide‐Ynamides via α‐Imino Copper Carbenes DOI
Xin Liu, Li‐Gao Liu,

Can‐Ming Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 14, 2023

[2,3]-Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle-Kirmse reaction) generated from metal carbenes represents one of the powerful methods for construction C(sp3 )-S and C-C bonds. Although significant advances have been achieved, asymmetric versions via generation ylides rarely reported to date, they so far limited diazo compounds as carbene precursors. Here, we describe a copper-catalyzed enantioselective Doyle-Kirmse azide-ynamide cyclization, leading practical divergent assembly an array chiral [1,4]thiazino[3,2-b]indoles bearing quaternary carbon stereocenter in generally moderate excellent yields enantioselectivities. Importantly, this protocol unique catalytic non-diazo approach unprecedented [2,3]-sigmatropic α-imino carbenes.

Language: Английский

Citations

30
Diastereo- and atroposelective synthesis of N-arylpyrroles enabled by light-induced phosphoric acid catalysis DOI Creative Commons
Lei Dai, Xueting Zhou, Jiami Guo

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 9, 2023

The C-N axially chiral N-arylpyrrole motifs are privileged scaffolds in numerous biologically active molecules and natural products, as well ligands/catalysts. Asymmetric synthesis of N-arylpyrroles, however, is still challenging, the simultaneous creation contiguous axial central chirality remains unknown. Herein, a diastereo- atroposelective N-arylpyrroles enabled by light-induced phosphoric acid catalysis has been developed. key transformation one-pot, three-component oxo-diarylation reaction, which simultaneously creates quaternary stereogenic center. A broad range unactivated alkynes were readily employed reaction partner this transformation, products obtained good yields, with excellent enantioselectivities very diastereoselectivities. Notably, skeletons represent interesting structural that could be used ligands catalysts asymmetric catalysis.

Language: Английский

Citations

29
Copper-Catalyzed Intermolecular [2 + 2 + 2] Annulation of Diynes with Alkynes: Construction of Carbazoles DOI
Zhentao Zhang,

Chen Luo,

Zhiyong Yu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Transition-metal-catalyzed [2 + 2 2] annulation of alkynes is an efficient pathway for the synthesis aromatic compounds. However, most established methods require noble metal catalysts. Herein, we report a copper-catalyzed intermolecular diynes with through vinyl cation intermediates, enabling atom-economical preparation biologically important carbazole skeletons. The reaction shows good regioselectivity in aryl(alkyl)alkynes. Moreover, preliminary results have also been obtained related catalytic atroposelective transformation. This represents rare example non-noble-metal-catalyzed ynamides pathway.

Language: Английский

Citations

1
Biocatalytic Atroposelective Synthesis of Axially Chiral N-Arylindoles via Dynamic Kinetic Resolution DOI
Patricia Rodríguez‐Salamanca, Gonzalo de Gonzalo, José A. Carmona

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 13(1), P. 659 - 664

Published: Dec. 22, 2022

A highly enantioselective biocatalytic dynamic kinetic resolution (DKR) of configurationally labile N-arylindole aldehydes is described. The DKR proceeds by atroposelective bioreduction the carbonyl group catalyzed commercial ketoreductases (KREDs), thus affording corresponding axially chiral aminoalcohols, with excellent conversions and optical purities. strategy relies on racemization stereogenic axis that takes place thanks to a transient Lewis pair interaction between NMe2 aldehyde groups. This protocol features broad substrate scope under very mild conditions.

Language: Английский

Citations

33
Atroposelective Synthesis of N-Arylindoles via Enantioselective N–H Bond Insertion DOI
Chao Niu, Yi Zhou, Qiang Chen

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(40), P. 7428 - 7433

Published: Oct. 3, 2022

We present here a rhodium-catalyzed asymmetric N-H insertion reaction, which is concerted process revealed by DFT calculations, for the synthesis of novel axially chiral N-arylindoles reaction between indoles and diazonaphthoquinones. The occurs at N1 rather than C2/C3 positions indoles, providing in good yields excellent enantiomeric ratios. Furthermore, this protocol also amenable to N-arylcarbazoles with enantiocontrol.

Language: Английский

Citations

29
Silver-Catalyzed Direct Nucleophilic Cyclization: Enantioselective De Novo Synthesis of C–C Axially Chiral 2-Arylindoles DOI

Liangbin Yu,

Junjun Liu,

Shiyu Xiang

et al.

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

Citations

22
Atroposelective Synthesis of Heterobiaryls through Ring Formation DOI

Huai‐Ri Sun,

Atif Sharif,

Jie Chen

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(27)

Published: March 6, 2023

Atropisomeric heterobiaryls play a vital role in natural products, chiral ligands, organocatalysts, and other research fields, which have aroused great interest from chemists recent years. Until now, growing number of optically active based on indole, quinoline, isoquinoline, pyridine, pyrrole, azole, benzofuran skeletons been successfully synthesized through metal or organic catalytic cross-coupling, functionalization prochiral racemic heterobiaryls, ring formation. Among different strategies for the atroposelective synthesis strategy formation has become tool toward this goal. In review, we summarize enantioselective axially approaches, such as cycloaddition, cyclization, chirality conversion. Meanwhile, reaction mechanism corresponding applications are also discussed.

Language: Английский

Citations

22
Asymmetric rhodium-catalyzed click cycloaddition to access C–N axially chiralN-triazolyl indoles DOI Creative Commons
Li Zhou, Yankun Li,

Shunian Li

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(19), P. 5182 - 5187

Published: Jan. 1, 2023

The copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction is regarded as a prime example of "click chemistry", but the asymmetric click internal alkynes still remains challenging. A new Rh-catalyzed N-alkynylindoles with azides was developed, providing atroposelective access to C-N axially chiral triazolyl indoles, type heterobiaryl, excellent yields and enantioselectivity. This approach efficient, mild, robust atom-economic, features very broad substrate scope easily available Tol-BINAP ligands.

Language: Английский

Citations

22
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

Citations

20
Organocatalytic atroposelective synthesis of axially chiral N,N′-pyrrolylindoles via de novo indole formation DOI Creative Commons

Cong-Shuai Wang,

Qi Xiong, Hui Xu

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(43), P. 12091 - 12097

Published: Jan. 1, 2023

The first organocatalytic atroposelective synthesis of axially chiral N,N'-pyrrolylindoles based on o-alkynylanilines was successfully established via de novo indole formation catalyzed by phosphoric acid (CPA). This new synthetic strategy introduced CPA-catalyzed asymmetric 5-endo-dig cyclization well-designed containing a pyrrolyl unit, resulting in wide range high yields with exclusive regioselectivity and excellent enantioselectivity (up to 99% yield, >20 : 1 rr, 95 5 er). Considering the potential biological significance N-N atropisomers, preliminary activity studies were performed revealed that these structurally important had low IC50 value promising impressive cytotoxicity against several kinds cancer cell lines. DFT reveal N-nucleophilic mediated CPA is rate- stereo-determining step, which ligand-substrate dispersion interactions facilitate axial chirality target products.

Language: Английский

Citations

19