Asymmetric Construction of Chiral 2‐Azetines and Axially Chiral Tetrasubstituted Allenes via Phosphine Catalysis DOI Open Access
Yi Tang, Mingxia Huang,

Jingrong Jin

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 11, 2024

Abstract Chiral 2‐azetines and allenes are highly valuable structural units in natural products useful chemicals. However, enantioselective synthesis of both has been extremely challenging. Herein, we present asymmetric construction chiral (70–98 % yields up to 96 ee) through phosphine‐catalyzed [2+2] annulation yne‐enones with sulfamate‐derived cyclic imines. These were easily transformed into upon treatment Et 3 SiH, BF ⋅ 2 O water at rt for minutes. Based on the above transformations, a concise one‐pot synthetic procedure combining imines under phosphine catalysis sequential reduction/isomerization/ring‐opening reaction was thus set up, providing axially tetrasubstituted satisfactory enantioselectivities (56–90 91 ee).

Language: Английский

Catalytic (4+2) Annulation via Regio‐ and Enantioselective Interception of in‐situ Generated Alkylgold Intermediate DOI
Ming Bao, Yi Zhou,

Haoxuan Yuan

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 22, 2024

A regio- and stereoselective stepwise (4+2) annulation of N-propargylamides α,β-unsaturated imines/ketones has been accomplished with synergetic catalysis by a combination gold-complex chiral quinine-derived squaramide (QN-SQA), leading to highly functionalized tetrahydropyridines/dihydropyrans in good high yields generally excellent enantioselectivity. Mechanistic studies DFT calculations indicate that the situ formed alkylgold species is key intermediate this transformation, amide group served as traceless directing selective transformation. This method complements enantioselective allene reagents, providing formal internal C-C π-bond cycloaddition products, which challenging remains elusive.

Language: Английский

Citations

2
Remote Enantioselective ε‐Alkylation of Copper Ethynylallenylidenes: Precise Control of Central and Axial Chirality DOI

Yu‐Hua Wen,

Minghao Liu, Yuhao Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Chiral tetrasubstituted allenes have emerged as important architectures for engineering biologically active compounds. The construction of unique allene scaffolds with precise control continuous central and axial chirality remains yet to be developed. Here, we report a remote enantioselective ϵ-alkylation yne-propargylic acetates enals enabled by NHC copper cooperative catalysis, leading series excellent enantioselectivities (up >99 % ee) diastereoselectivities >95 : 5 dr). This method features high regioselectivity simultaneous chirality. Mechanistic studies suggest activation mode synergistic distal created from the ethynylallenylidenes.

Language: Английский

Citations

2
Asymmetric Construction of Chiral 2‐Azetines and Axially Chiral Tetrasubstituted Allenes via Phosphine Catalysis DOI Open Access
Yi Tang, Mingxia Huang,

Jingrong Jin

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 11, 2024

Chiral 2-azetines and allenes are highly valuable structural units in natural products useful chemicals. However, enantioselective synthesis of both has been extremely challenging. Herein, we present asymmetric construction chiral (70-98 % yields up to 96 ee) through phosphine-catalyzed [2+2] annulation yne-enones with sulfamate-derived cyclic imines. These were easily transformed into upon treatment Et

Language: Английский

Citations

1
Catalytic (4+2) Annulation via Regio‐ and Enantioselective Interception of in‐situ Generated Alkylgold Intermediate DOI
Ming Bao, Yi Zhou,

Haoxuan Yuan

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)

Published: May 22, 2024

Abstract A regio‐ and stereoselective stepwise (4+2) annulation of N ‐propargylamides α,β‐unsaturated imines/ketones has been accomplished with synergetic catalysis by a combination gold‐complex chiral quinine‐derived squaramide (QN‐SQA), leading to highly functionalized tetrahydropyridines/dihydropyrans in good high yields generally excellent enantioselectivity. Mechanistic studies DFT calculations indicate that the situ formed alkylgold species is key intermediate this transformation, amide group served as traceless directing selective transformation. This method complements enantioselective allene reagents, providing formal internal C−C π‐bond cycloaddition products, which challenging remains elusive.

Language: Английский

Citations

0
Remote Enantioselective ε‐Alkylation of Copper Ethynylallenylidenes: Precise Control of Central and Axial Chirality DOI

Yu‐Hua Wen,

Minghao Liu, Yuhao Wang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Abstract Chiral tetrasubstituted allenes have emerged as important architectures for engineering biologically active compounds. The construction of unique allene scaffolds with precise control continuous central and axial chirality remains yet to be developed. Here, we report a remote enantioselective ϵ‐alkylation yne‐propargylic acetates enals enabled by NHC copper cooperative catalysis, leading series excellent enantioselectivities (up >99 % ee) diastereoselectivities >95 : 5 dr). This method features high regioselectivity simultaneous chirality. Mechanistic studies suggest activation mode synergistic distal created from the ethynylallenylidenes.

Language: Английский

Citations

0
Asymmetric Construction of Chiral 2‐Azetines and Axially Chiral Tetrasubstituted Allenes via Phosphine Catalysis DOI Open Access
Yi Tang, Mingxia Huang,

Jingrong Jin

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 11, 2024

Abstract Chiral 2‐azetines and allenes are highly valuable structural units in natural products useful chemicals. However, enantioselective synthesis of both has been extremely challenging. Herein, we present asymmetric construction chiral (70–98 % yields up to 96 ee) through phosphine‐catalyzed [2+2] annulation yne‐enones with sulfamate‐derived cyclic imines. These were easily transformed into upon treatment Et 3 SiH, BF ⋅ 2 O water at rt for minutes. Based on the above transformations, a concise one‐pot synthetic procedure combining imines under phosphine catalysis sequential reduction/isomerization/ring‐opening reaction was thus set up, providing axially tetrasubstituted satisfactory enantioselectivities (56–90 91 ee).

Language: Английский

Citations

0