Ligand-controlled divergent asymmetric C(sp3)−H and C(sp3)−O insertion via vinyl cations DOI Creative Commons

Cui‐Ting Li,

Li‐Gao Liu,

Jia-Zheng Li

et al.

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

Published: May 2, 2025

The insertion of either C-H bond or C-O via cleavage has proven to be a very attractive strategy for the construction C-C and bonds in organic synthesis. However, such divergent catalytic asymmetric reactions selective formation C(sp3)-H formal C(sp3)-O products from same precursors are rarely explored. Herein, we report ligand-controlled reaction vinyl cations by non-diazo approach, leading practical atom-economical assembly range chiral spiro fused polycyclic pyrroles generally moderate excellent yields with chemo- enantioselectivities. Importantly, this protocol not only represents rare example successful reaction, but also constitutes an enantioselective 1,6-C-H carbenoid into acetals approach.

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
Biocatalytic One-Carbon Ring Expansion of Aziridines to Azetidines via a Highly Enantioselective [1,2]-Stevens Rearrangement DOI
David C. Miller,

Ravi Lal,

Luca Marchetti

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(11), P. 4739 - 4745

Published: March 8, 2022

We report enantioselective one-carbon ring expansion of aziridines to make azetidines as a new-to-nature activity engineered "carbene transferase" enzymes. A laboratory-evolved variant cytochrome P450BM3, P411-AzetS, not only exerts unparalleled stereocontrol (99:1 er) over [1,2]-Stevens rearrangement but also overrides the inherent reactivity aziridinium ylides, cheletropic extrusion olefins, perform rearrangement. By controlling fate highly reactive ylide intermediates, these evolvable biocatalysts promote transformation which cannot currently be performed using other catalyst classes.

Language: Английский

Citations

56
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

44
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

34
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

33
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

31
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

13
Chiral Brønsted acid-catalyzed asymmetric intermolecular [4 + 2] annulation of ynamides with para-quinone methides DOI

Hang‐Hao Li,

Ya-Nan Meng,

Can‐Ming Chen

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(5), P. 1467 - 1473

Published: April 12, 2023

Language: Английский

Citations

19
Asymmetric formal C–C bond insertion into aldehydes via copper-catalyzed diyne cyclization DOI Creative Commons

Cui‐Ting Li,

Linjun Qi, Li‐Gao Liu

et al.

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

Published: Nov. 3, 2023

The formal C-C bond insertion into aldehydes is an attractive methodology for the assembly of homologated carbonyl compounds. However, homologation has been limited to diazo approach and enantioselective reaction was rarely developed. Herein, we report asymmetric through diyne cyclization strategy. In presence Cu(I)/SaBOX catalyst, this method leads efficient construction versatile axially chiral naphthylpyrroles in moderate excellent yields with good enantioselectivities. This protocol represents a rare example using non-diazo approach. combined experimental computational mechanistic studies reveal mechanism, origin regioselectivity stereoselectivity. Notably, phosphine ligand derived from synthesized skeleton proven be applicable catalysis.

Language: Английский

Citations

18