Enantioselective Construction of Quaternary Stereocenters via A Chiral Spiro Phosphoric Acid-Assisted Formal Gold Carbene gem-Dialkylation Reaction DOI
Ke-Wei Chen,

Su Zhou,

Chao Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19261 - 19270

Published: July 1, 2024

Enantioselective construction of all-carbon quaternary stereocenters has attracted much attention over the past few decades. A variety catalytic asymmetric methods have been disclosed based on use presynthesized complex reagents that impart congested steric hindrance to reaction center, which generally produce chiral molecules through forming one C-C bond. The readily available could build two bonds same carbonic center with concomitant assembly remains challenging. Herein, we disclose a alkyne multifunctionalization using gold and spiro phosphoric acid (SPA) for synergistic catalysis. In this method, accessible internal alkynes served as key carbene precursors, followed by

Language: Английский

Enantioselective Copper‐Catalyzed Formal [2+1] and [4+1] Annulations of Diynes with Ketones via Carbonyl Ylides DOI
Linjun Qi,

Cui‐Ting Li,

Zheng‐Qi Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(43)

Published: Aug. 17, 2022

Carbonyl ylides have proven to be powerful synthons for the efficient construction of various valuable O-heterocycles, and formation carbonyl by reaction metal carbenes with carbonyls has attracted increasing attention over past decades. However, a catalyst-controlled highly enantioselective from is extremely challenging. Herein, we report novel copper-catalyzed asymmetric formal [2+1] [4+1] annulations diynes ketones via ylides. Importantly, this protocol not only represents first example successful epoxidation ylides, but also constitutes vinyl cations compounds. This method leads divergent, practical atom-economical synthesis range chiral oxiranes dihydrofurans in moderate excellent yields generally enantioselectivities diastereoselectivities remote-stereocontrol strategy.

Language: Английский

Citations

42
Catalyst‐Dependent Stereospecific [3,3]‐Sigmatropic Rearrangement of Sulfoxide‐Ynamides: Divergent Synthesis of Chiral Medium‐Sized N,S‐Heterocycles DOI
Guang‐Yu Zhu,

Ji‐Jia Zhou,

Li‐Gao Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(28)

Published: April 27, 2022

Medium-sized N,S-heterocycles have received tremendous interest due to their biological activities and potential medical applications. However, asymmetric synthesis of these compounds are extremely rare. Described herein is a catalyst-dependent [3,3]-sigmatropic rearrangement sulfoxide-ynamides, enabling divergent atom-economic series valuable medium-sized in moderate good yields with broad substrate scope. Importantly, excellent enantioselectivities been achieved via an unprecedented chirality-transfer. Moreover, theoretical calculations employed elucidate the origins stereospecific [3,3]-rearrangement.

Language: Английский

Citations

40
Construction of Axially Chiral Arylpyrroles via Atroposelective Diyne Cyclization DOI

Yang‐Bo Chen,

Li‐Gao Liu,

Can‐Ming Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: March 30, 2023

Axially chiral biaryls widely exist in natural products and pharmaceuticals are used as ligands catalysts asymmetric synthesis. Compared to the well-established axially 6-membered biaryl skeletons, examples of 5-membered have been quite scarce, mono-substituted 3-arylpyrrole atropisomers not reported. Here, we disclose a copper-catalyzed atroposelective diyne cyclization for construction range arylpyrrole good excellent yields with generally enantioselectivities via oxidation X-H insertion vinyl cations. Importantly, this protocol only represents first synthesis atropisomers, but also constitutes example atropisomer Theoretical calculations further support mechanism cation-involved elucidate origin enantioselectivity.

Language: Английский

Citations

32
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
Recent advances in the construction of axially chiral arylpyrroles DOI

Yang‐Bo Chen,

Ye-Nan Yang,

Xuan-Zhu Huo

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(9), P. 2480 - 2491

Published: Aug. 9, 2023

Language: Английский

Citations

30
Enantioselective functionalization of unactivated C(sp3)–H bonds through copper-catalyzed diyne cyclization by kinetic resolution DOI Creative Commons

Yang‐Bo Chen,

Li‐Gao Liu,

Zhe-Qi Wang

et al.

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

Published: March 12, 2024

Site- and stereoselective C-H functionalization is highly challenging in the synthetic chemistry community. Although of vinyl cations has been vigorously studied C(sp

Language: Английский

Citations

11
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
Copper-catalyzed asymmetric cyclization of alkenyl diynes: method development and new mechanistic insights DOI Creative Commons
Xin‐Qi Zhu,

Pan Hong,

Yan-Xin Zheng

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(27), P. 9466 - 9474

Published: Jan. 1, 2021

A copper-catalyzed asymmetric cyclization of alkenyl diynes involving a vinylic C(sp2)–H functionalization is reported, enabling the construction various valuable chiral polycyclic-pyrroles in high yields and enantioselectivities.

Language: Английский

Citations

54
Radical Reactions of Ynamides DOI
Tong‐De Tan, Ze‐Shu Wang, Peng‐Cheng Qian

et al.

Small Methods, Journal Year: 2020, Volume and Issue: 5(3)

Published: Sept. 29, 2020

Ynamides are electron-rich heteroatom-substituted alkynes with C-C triple bond directly tethered to the amide group. Over past decades, ynamides have proven be versatile reagents for organic synthesis and received extensive attention. Compared well-established ionic reactions of ynamides, radical-based ynamide been exploited relatively seldom. Herein, radical classified by attack at α-position β-position reviewed highlighting reaction selectivity, scope, mechanism, applicability. The aim this review is provide a comprehensive summarization these advances, casting light on further development chemistry.

Language: Английский

Citations

53
Gold‐Catalyzed Transformation of Ynamides DOI

Shashank Shandilya,

Manash Protim Gogoi, Shubham Dutta

et al.

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(12), P. 4123 - 4149

Published: Aug. 25, 2021

Ynamide, a unique species with inherited polarization of nitrogen lone pair electron to triple bond, has been largely used for the developement novel synthetic methods and construction unusual N-bearing heterocycles. The reaction versatility ynamide on umpolung reactivity, radical reactions asymmetric synthesis have recently reviewed. This review provides an overall scenic view into gold catalyzed transformation ynamides. ynamides reactivity towards nitrogen-transfer reagents, such as azides, ylides, isoxazoles, anthranils; oxygen atom-transfer like nitrones, sulfoxides, pyridine N-oxides; carbon nucleophiles under catalysis are herein uncovered. scope well mechanistic insights each is also briefed.

Language: Английский

Citations

49