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, Journal Year: 2023, Volume and Issue: 135(10)

Published: Jan. 14, 2023

Abstract [2,3]‐Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle–Kirmse reaction) generated from metal carbenes represents one of the powerful methods for construction C(sp 3 )−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

Synthesis of Axially ChiralN‐Arylindoles via Atroposelective Cyclization of Ynamides Catalyzed by Chiral Brønsted Acids DOI
Ze‐Shu Wang,

Lu‐Jing Zhu,

Cui‐Ting Li

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(20)

Published: March 5, 2022

In recent years, asymmetric catalysis of ynamides has attracted much attention, but these reactions mostly constructed central chirality, except for a few examples on the synthesis axially chiral compounds which exclusively relied noble-metal catalysis. Herein, facile access to N-heterocycles enabled by Brønsted acid-catalyzed 5-endo-dig cyclization is disclosed, represents first metal-free protocol construction from ynamides. This method allows practical and atom-economical valuable N-arylindoles in excellent yields with generally enantioselectivities. Moreover, organocatalysts ligands based such N-arylindole skeletons are demonstrated be applicable

Language: Английский

Citations

83
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

43
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
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
Stereoselective Synthesis of Polysubstituted Conjugated Dienes Enabled by Photo‐Driven Sequential Sigmatropic Rearrangement DOI
Xin Ji, Chaoren Shen,

Yuhao Ni

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 8, 2024

We here reported a highly stereoselective method for the synthesis of polysubstituted conjugated dienes from α-aryl α-diazo alkynyl ketones and pyrazole-substituted unsymmetric aminals under mild conditions, which was promoted by photo-irridation involved with 1,6-dipolar intermediate quadruple sigmatropic rearrangements, successfully developed. In this transformation, cleavage four bonds recombination five were implemented in one operational step. This protocol provided modular tool constructing amines, pyrazoles α-alkynyl-α-diazoketones one-pot manner. The results mechanistic investigation indicated that plausible reaction path underwent 1,6-sigmatropic rearrangement instead 1,5-sigmatropic rearrangement.

Language: Английский

Citations

6
Synthesis of Axially ChiralN‐Arylindoles via Atroposelective Cyclization of Ynamides Catalyzed by Chiral Brønsted Acids DOI
Ze‐Shu Wang,

Lu‐Jing Zhu,

Cui‐Ting Li

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(20)

Published: March 5, 2022

Abstract In recent years, asymmetric catalysis of ynamides has attracted much attention, but these reactions mostly constructed central chirality, except for a few examples on the synthesis axially chiral compounds which exclusively relied noble‐metal catalysis. Herein, facile access to N ‐heterocycles enabled by Brønsted acid‐catalyzed 5‐ endo ‐ dig cyclization is disclosed, represents first metal‐free protocol construction from ynamides. This method allows practical and atom‐economical valuable ‐arylindoles in excellent yields with generally enantioselectivities. Moreover, organocatalysts ligands based such ‐arylindole skeletons are demonstrated be applicable

Language: Английский

Citations

11
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, Journal Year: 2022, Volume and Issue: 134(28)

Published: April 27, 2022

Abstract 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

10
Ag(I)-Promoted, Diastereoselective Cyclo-isomerization of N-Alkynyl-7-azaindole-2-carbinols. Selective Synthesis of syn-1,2-Diarylpyrrolo[1,2-a]indol-3-ones and (Z)-8-Benzylideneoxazolo[3′,4′’:1,5]pyrrolo[2,3-b]pyridines DOI
Bhavna Yadav, Beeraiah Baire

Organic Letters, Journal Year: 2022, Volume and Issue: 24(29), P. 5450 - 5455

Published: July 14, 2022

The design and development of an Ag(I)-promoted, highly diastereoselective cycloisomerization strategy for the synthesis syn-1,2-diarylpyrrolo[1,2-a]indol-3-ones from N-alkynyl-indole-2-carbinols is reported. H218O control experiment identification 18O-labeled product suggested involvement external water. 7-azaindole substrates showned a distinct reactivity to give (Z)-8-benzylideneoxazolo[3′,4′:1,5]pyrrolo[2,3-b]pyridines. Key features this are its 100% atom economy, access important heterocycles, diverse substrate scope, yields up 95%, operationally simple procedure, indole vs 7-azaindoles.

Language: Английский

Citations

9
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, Journal Year: 2022, Volume and Issue: 134(43)

Published: Aug. 17, 2022

Abstract 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

5
Mechanistic Insight into Palladium/Brønsted Acid Catalyzed Methoxycarbonylation and Hydromethoxylation of Internal Alkene: A Computational Study DOI

Lingli Han,

Kang Lv, Teng Wang

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(9), P. 3904 - 3915

Published: Feb. 17, 2023

Density functional theory (DFT) calculations were performed to study the palladium/Brønsted acid-catalyzed methoxycarbonylation and hydromethoxylation reactions of internal alkene. The calculated results show that pyridyl group (N atom) in bidentate phosphine ligand with built-in base (L1) plays a crucial role controlling selectivity. With help group, methanolysis steps reaction become easy, both linear ester methyl 3,4-dimethylpentanoate (P1) product 2-methoxy-2,3-dimethylbutane (P2) could be obtained. In contrast, possibility leading branched P1′ was ruled out according our calculations. steric effect account for observed presence DPEphos (L2) does not bear step becomes rate-determining high overall energy barrier. Neither nor generated. acid co-catalyzed also difficult without assistance L2 ligand. Instead, TsOH-catalyzed take place generate ether P2.

Language: Английский

Citations

2