Empowering Diastereoselective Cyclopropanation of Unactivated Alkenes with Sulfur Ylides through Nucleopalladation DOI

Nityananda Ballav,

Chandan Kumar Giri, Shib Nath Saha

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 7, 2025

Regio- and stereoselective cyclopropanation of unactivated alkenes under mild conditions remains a challenging yet fundamental transformation. We present versatile palladium(II)-catalyzed method for the diastereoselective alkenyl amines acids, which leverages nucleopalladation mechanism unique ambiphilic reactivity sulfur ylides. This Pd(II)/Pd(IV) catalytic protocol selectively delivers anti-cyclopropanes allylamines with removable isoquinoline-1-carboxamide auxiliary, while enabling excellent syn-selectivity acid derivatives containing 2-(aminomethyl)pyridine derivative as directing group. The is operationally simple scalable, features wide substrate generality, also effective in presence various medicinally relevant scaffolds. cyclopropane products were further transformed into 1,2,3-trifunctionalized cyclopropanes engaged an aza-Piancatelli reaction, introducing additional molecular complexity. DFT studies performed to shed light on reaction origins observed stereoselectivity.

Язык: Английский

Nickel-Catalyzed Three-Component Carboamination/Cyclization of Alkynes To Access 2,3-Disubstituted Quinolines DOI
Yang Gao, Jiale Xing, Yanping Huo

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

Presented herein is a nickel-catalyzed chemo- and regioselective three-component tandem carboamination cyclization of terminal alkynes with organoboronic acids anthranils for facile modular access to 2,3-substituted quinolines. In this process, anthranil has dual roles: serving as an electrophilic aminating reagent redox buffer suppress the generation off-cycle Ni(0) complex. Moreover, anionic acetylacetonate (acac) ligand was found be vital ensure productive Ni(I)-Ni(III)-Ni(I) catalytic cycle.

Язык: Английский

Процитировано

0
Modular Construction of Chiral Aminopiperidine via Palladium-Catalyzed Hydroamination of 1,2-Dihydropyridine DOI
Qian Wang, Shouyou Huang,

Lifei Nie

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 12, 2025

In this study, we describe a generally straightforward methodology for the catalytic synthesis of chiral aminopiperidine from pyridine and azoles. The key step was palladium-catalyzed regioselective N–H insertion into double bond 1,2-dihydropyridine. This hydroamination exhibits wide substrate scope functional group compatibility. Mechanistic study revealed that C═C followed cis addition. utility protocol demonstrated by diverse functionalization enamine bond.

Язык: Английский

Процитировано

0
Palladium(II)-Catalyzed Regioselective Hydroamination of Allylamines to N-Alkyl Sulfoximines DOI
Shib Nath Saha,

Nityananda Ballav,

Mahiuddin Baidya

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 14, 2025

An intermolecular coupling between sulfoximines and allyl amines, linked to the picolinamide directing group, is developed by leveraging a nucleopalladation-guided regioselective hydroamination strategy, enabling production of range valuable N-alkyl in high yields. The protocol features operational simplicity broad substrate scope was also amenable aniline nucleophiles. Synthetic utilities were showcased through scale-up reactions product diversifications, leading biorelevant molecules.

Язык: Английский

Процитировано

0
Empowering Diastereoselective Cyclopropanation of Unactivated Alkenes with Sulfur Ylides through Nucleopalladation DOI

Nityananda Ballav,

Chandan Kumar Giri, Shib Nath Saha

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 7, 2025

Regio- and stereoselective cyclopropanation of unactivated alkenes under mild conditions remains a challenging yet fundamental transformation. We present versatile palladium(II)-catalyzed method for the diastereoselective alkenyl amines acids, which leverages nucleopalladation mechanism unique ambiphilic reactivity sulfur ylides. This Pd(II)/Pd(IV) catalytic protocol selectively delivers anti-cyclopropanes allylamines with removable isoquinoline-1-carboxamide auxiliary, while enabling excellent syn-selectivity acid derivatives containing 2-(aminomethyl)pyridine derivative as directing group. The is operationally simple scalable, features wide substrate generality, also effective in presence various medicinally relevant scaffolds. cyclopropane products were further transformed into 1,2,3-trifunctionalized cyclopropanes engaged an aza-Piancatelli reaction, introducing additional molecular complexity. DFT studies performed to shed light on reaction origins observed stereoselectivity.

Язык: Английский

Процитировано

0