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

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(44)

Опубликована: Авг. 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.

Язык: Английский

Chemodivergent Tandem Hydroalkylation and Hydroalkenoxylation of Conjugated Enynes DOI

Bo-Yuan Xie,

Zhi‐Tao He

ACS Catalysis, Год журнала: 2024, Номер 14(13), С. 9742 - 9751

Опубликована: Июнь 14, 2024

Due to the instability and weak O-nucleophilicity of enol, carbonyl compounds prefer function as C-nucleophiles instead O-nucleophiles in extensively studied transition metal-catalyzed hydrofunctionalizations unsaturated bonds. The corresponding hydroalkenoxylation reaction has thus long been unexplored. Here, we describe a chemodivergent protocol for challenging reactions. Dictated by Pd catalyst bearing different ligands, both 5-exo-trig 6-endo-trig processes are demonstrated be feasible between 1,3-enynes ketoesters, polysubstituted hydrofurans hydropyrans achieved good yields excellent chemoselectivities. In addition, enantioselective is also explored under an Rh moderate efficiency but with high stereoselectivities. Mechanistic studies corroborate designed tandem hydroalkylation uncover that ligand-to-ligand hydrogen transfer process might involved turnover-limiting step hydroalkenoxylation.

Язык: Английский

Процитировано

5
Transition Metal-Catalyzed Asymmetric Migratory Allylic C—H Functionalization of Remote Dienes DOI
Jingming Zhang, Zhi‐Tao He

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(2), С. 592 - 592

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0
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

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(44)

Опубликована: Авг. 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.

Язык: Английский

Процитировано

3
Stereoselective Synthesis of Polysubstituted Dihydropyrroles via 1,5‐Addition and N‐1,4‐Addition Cascade DOI

J. ZHANG,

Yuchao Wang, Liang Chen

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(38)

Опубликована: Май 3, 2024

An unprecedented 1,5-addition/N-1,4-addition cascade reaction is established via palladium hydride catalysis. A variety of polysubstituted dihydropyrrole skeletons are constructed in high yield and with exclusively >20 : 1 diastereoselectivity. enantioselective protocol this design also developed to provide a novel access enantioenriched dihydropyrroles.

Язык: Английский

Процитировано

1
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

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(44)

Опубликована: Авг. 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.

Язык: Английский

Процитировано

0