Palladium-Catalyzed Enantioselective β-Hydride Elimination for the Construction of Remote Stereocenters DOI Creative Commons
Weiwei Zi, Shaozi Sun, Shengnan Sun

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 21, 2024

Abstract The β-H elimination is a crucial elementary step in transition-metal catalysis, but controlling the stereochemistry of this process has been underdeveloped. limited works reported so far have only focused on creating axial chirality allenes, and no report able to build central using asymmetric elimination. In study, we Trost ligand-enabled enantioselective desymmetric reaction from π-allyl-Pd. This transformation provides rapid access cyclohexenes bearing C4-remoted stereocenter, total synthesis (-)-oleuropeic acid (-)-7-hydroxylterpineol was demonstrated. Computational studies shown that rate-determining step, non-covalent interactions between amide moiety ligand benzene cyclohexane moieties substrate play key role stereocontrol during

Language: Английский

Palladium(0) and Brønsted Acid Co‐catalyzed Enantioselective Hydro‐Cyclization of 2,4‐Dienyl Hydrazones and Oximes DOI Open Access
Yufan Li,

Wu-Tao Gui,

Fu Pi

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: Aug. 6, 2024

Abstract The transition metal‐catalyzed asymmetric hydro‐functionalization of 1,3‐dienes has been well explored, but most reactions focus on electron‐neutral substrates in an intermolecular manner. Here we first demonstrate that readily available 2,4‐dienyl hydrazones and oximes can be efficiently utilized the hydro‐cyclization reaction under co‐catalysis a Brønsted acid chiral palladium complex, furnishing multifunctional dihydropyrazones dihydroisoxazoles, respectively. Diverse substitution patterns for both types electron‐deficient diene compounds are tolerated, corresponding heterocycles were generally constructed with moderate to excellent enantioselectivity, which elaborated access products higher molecular complexity diversity. Control experiments density functional theory calculations support α‐regioselective protonation dienyl by concurrent π‐Lewis base activation Pd 0 complex is energetically favoured formation active π‐allylpalladium intermediates, outer‐sphere allylic amination or etherification mode adopted deliver observed cyclized enantioselectively.

Language: Английский

Citations

3
Palladium-catalyzed enantioselective β-hydride elimination for the construction of remote stereocenters DOI Creative Commons
Shaozi Sun, Shengnan Sun, Weiwei Zi

et al.

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

Published: March 5, 2025

The β-H elimination is a crucial elementary step in transition-metal catalysis, but controlling the stereochemistry of this process has been underdeveloped. limited works reported so far have only focused on creating axial chirality allenes, and no report able to build central using asymmetric elimination. In study, we Trost ligand-enabled enantioselective desymmetric reaction from π-allyl-Pd. This transformation provides rapid access cyclohexenes bearing C4-remoted stereocenter, total synthesis (-)-oleuropeic acid (-)-7-hydroxyterpineol demonstrated. Computational studies shown that rate-determining step, non-covalent interactions between amide moiety ligand benzene cyclohexane moieties substrate play key role stereocontrol during

Language: Английский

Citations

0
Palladium(0) and Brønsted Acid Co‐catalyzed Enantioselective Hydro‐Cyclization of 2,4‐Dienyl Hydrazones and Oximes DOI
Yufan Li,

Wu-Tao Gui,

Fu Pi

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: Aug. 6, 2024

Abstract The transition metal‐catalyzed asymmetric hydro‐functionalization of 1,3‐dienes has been well explored, but most reactions focus on electron‐neutral substrates in an intermolecular manner. Here we first demonstrate that readily available 2,4‐dienyl hydrazones and oximes can be efficiently utilized the hydro‐cyclization reaction under co‐catalysis a Brønsted acid chiral palladium complex, furnishing multifunctional dihydropyrazones dihydroisoxazoles, respectively. Diverse substitution patterns for both types electron‐deficient diene compounds are tolerated, corresponding heterocycles were generally constructed with moderate to excellent enantioselectivity, which elaborated access products higher molecular complexity diversity. Control experiments density functional theory calculations support α‐regioselective protonation dienyl by concurrent π‐Lewis base activation Pd 0 complex is energetically favoured formation active π‐allylpalladium intermediates, outer‐sphere allylic amination or etherification mode adopted deliver observed cyclized enantioselectively.

Language: Английский

Citations

0
Palladium-Catalyzed Enantioselective β-Hydride Elimination for the Construction of Remote Stereocenters DOI Creative Commons
Weiwei Zi, Shaozi Sun, Shengnan Sun

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 21, 2024

Abstract The β-H elimination is a crucial elementary step in transition-metal catalysis, but controlling the stereochemistry of this process has been underdeveloped. limited works reported so far have only focused on creating axial chirality allenes, and no report able to build central using asymmetric elimination. In study, we Trost ligand-enabled enantioselective desymmetric reaction from π-allyl-Pd. This transformation provides rapid access cyclohexenes bearing C4-remoted stereocenter, total synthesis (-)-oleuropeic acid (-)-7-hydroxylterpineol was demonstrated. Computational studies shown that rate-determining step, non-covalent interactions between amide moiety ligand benzene cyclohexane moieties substrate play key role stereocontrol during

Language: Английский

Citations

0