FeCl2-Mediated Rearrangement of Aminoperoxides into Functionalized Tetrahydrofurans: Dynamic Non-innocence of O-Ligands at an Fe Center Coordinates a Radical Cascade DOI

Yulia Yu. Belyakova,

Peter S. Radulov, Роман А. Новиков

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 27, 2024

The selective reaction of cyclic aminoperoxides with FeCl2 proceeds through a sequence O–O and C–C bond cleavages, followed by intramolecular cyclization, yielding functionalized tetrahydrofurans in 44–82% yields. Replacing the peroxyacetal group peroxide structure peroxyaminal fragment fundamentally alters pathway. Instead producing linear ketones, this modification leads to formation hard-to-access substituted tetrahydrofurans. Although aminoperoxide cores undergo multiple scissions, cascade is atom-economical. Computational analysis shows that O-ligands at Fe center have enough radical character promote fragmentation subsequent cyclization. stereoelectronic flexibility oxygen, combined iron's capacity stabilize reactive intermediates during multistep cascade, explains efficiency new atom-economic rearrangement.

Язык: Английский

Deacylative Homolysis of Ketone C(sp3)–C(sp2) Bonds: Streamlining Natural Product Transformations DOI
Michal Šimek, Sujit Mahato,

Brady W. Dehnert

и другие.

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

Опубликована: Янв. 7, 2025

The homolytic cleavage of C–C bonds adjacent to specific functional groups has lately emerged as a versatile approach for molecular diversification. Despite the ubiquity and synthetic utility ketones, radical fragmentation their α-C–C proven be formidable challenge. Here, we present broadly applicable deacylative strategy designed homolytically cleave aliphatic ketones various complexities, including transformations cycloalkanones into carboxylic acids tethered C-centered free radicals that can engaged in diverse radical-based processes. method involves ketone activation through treatment with hydrogen peroxide, yielding gem-dihydroperoxides. Subsequent single-electron-transfer reduction mediated by low-valent metal complex generates alkyl captured selectively radicophile choice, catalytic cross-coupling. logic our functionalization is exemplified total synthesis 14 natural products, one analogue, two drugs starting from readily available showcasing its transformative power settings. This obviates need reagents allows controlled conversion reconstructed making process highly across spectrum domains.

Язык: Английский

Процитировано

1
Halodealkenylation: Ozonolysis and Catalytic FeII with Vitamin C Convert C(sp3)–C(sp2) Bonds to C(sp3)–Halide Bonds DOI

Brady W. Dehnert,

Youwei Yin,

Ohyun Kwon

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 9, 2024

As part of our investigations into C-C bond scission and functionalization, we report a halodealkenylation in which the C(sp

Язык: Английский

Процитировано

2
FeCl2-Mediated Rearrangement of Aminoperoxides into Functionalized Tetrahydrofurans: Dynamic Non-innocence of O-Ligands at an Fe Center Coordinates a Radical Cascade DOI

Yulia Yu. Belyakova,

Peter S. Radulov, Роман А. Новиков

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 27, 2024

The selective reaction of cyclic aminoperoxides with FeCl2 proceeds through a sequence O–O and C–C bond cleavages, followed by intramolecular cyclization, yielding functionalized tetrahydrofurans in 44–82% yields. Replacing the peroxyacetal group peroxide structure peroxyaminal fragment fundamentally alters pathway. Instead producing linear ketones, this modification leads to formation hard-to-access substituted tetrahydrofurans. Although aminoperoxide cores undergo multiple scissions, cascade is atom-economical. Computational analysis shows that O-ligands at Fe center have enough radical character promote fragmentation subsequent cyclization. stereoelectronic flexibility oxygen, combined iron's capacity stabilize reactive intermediates during multistep cascade, explains efficiency new atom-economic rearrangement.

Язык: Английский

Процитировано

1