Redox-Neutral Umpolung Synthesis of α-Functionalized Amides DOI Creative Commons

Rui Wang,

Shaokang An,

Yi-Xuan Xin

и другие.

JACS Au, Год журнала: 2024, Номер 4(11), С. 4435 - 4444

Опубликована: Окт. 26, 2024

α-Heteroatom-substituted amides are useful as both targets and intermediates but challenging to synthesize via conventional enolate chemistry. Herein, we describe a general unified umpolung procedure prepare α-heteroatom-functionalized secondary with various heteroatom-based nucleophiles under redox-neutral conditions. This transformation is formal oxidation state reshuffle process from −N −C in the hydroxamate, thereby achieving α-heterofunctionalization of carbonyl groups without external oxidants. Regulated by mechanism, functionalization exclusively occurs at α-position hydroxamate precisely affords α-functionalized amide reliable predictability even complex settings. Density functional theory studies support that soft enolization enabled Mg2+/DIPEA combination essential facilitate formation α-lactam intermediate. represents first protocol amides.

Язык: Английский

Mechanistic Pathways in Cyanide-Mediated Benzoin Condensation: A Comprehensive Electron Localisation Function (ELF) and Catastrophe Theory Analysis of the Umpolung Reaction DOI Creative Commons
Michał Michalski, Sławomir Berski

Molecules, Год журнала: 2025, Номер 30(2), С. 378 - 378

Опубликована: Янв. 17, 2025

This research investigates the mechanism of cyanide-type umpolung reaction in benzoin condensation using topological analysis ELF and catastrophe theory. The study achieves a comprehensive understanding evolution chemical bonds non-bonding electron density benzaldehyde cyanide ions. results reveal that proceeds through five transition state structures, with formation Lapworth’s cyanohydrin being rate-determining step. characterises catastrophes field provides detailed description reaction. An in-depth confirms well-established Lapworth mechanism.

Язык: Английский

Процитировано

0
Enzyme-Catalyzed Umpolung Strategy for the Green Synthesis of Schiff bases and their Derivatives DOI
Taimur Khan,

Daixi Wang,

khan Bahadar

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

In organic chemistry, the umpolung reaction is an important concept that significantly expands chemical space and provides unique structures.

Язык: Английский

Процитировано

0
Green and efficient choline hydroxide-promoted C(sp3)-H selenation of arylacetamides at room temperature DOI
Jun-Bo Wang,

Yu Guan,

Bo-Xuan Huo

и другие.

Molecular Catalysis, Год журнала: 2024, Номер 567, С. 114452 - 114452

Опубликована: Авг. 15, 2024

Язык: Английский

Процитировано

1
Redox-Neutral Umpolung Synthesis of α-Functionalized Amides DOI Creative Commons

Rui Wang,

Shaokang An,

Yi-Xuan Xin

и другие.

JACS Au, Год журнала: 2024, Номер 4(11), С. 4435 - 4444

Опубликована: Окт. 26, 2024

α-Heteroatom-substituted amides are useful as both targets and intermediates but challenging to synthesize via conventional enolate chemistry. Herein, we describe a general unified umpolung procedure prepare α-heteroatom-functionalized secondary with various heteroatom-based nucleophiles under redox-neutral conditions. This transformation is formal oxidation state reshuffle process from −N −C in the hydroxamate, thereby achieving α-heterofunctionalization of carbonyl groups without external oxidants. Regulated by mechanism, functionalization exclusively occurs at α-position hydroxamate precisely affords α-functionalized amide reliable predictability even complex settings. Density functional theory studies support that soft enolization enabled Mg2+/DIPEA combination essential facilitate formation α-lactam intermediate. represents first protocol amides.

Язык: Английский

Процитировано

0