Phenothiazine Sulfoxides as Active Photocatalysts for the Synthesis of γ-Lactones DOI Creative Commons
Niklas Hölter,

Nils Rendel,

Leander Spierling

и другие.

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

Опубликована: Апрель 2, 2025

N-substituted phenothiazines are prominent and highly effective organic photoredox catalysts, particularly known for their strong reducing capabilities. Despite wide utility, the closely related phenothiazine sulfoxides, which easily form upon oxidation, have been largely overlooked not explored in context of photocatalysis. Herein, we describe discovery application N-phenylphenothiazine sulfoxide as a photocatalyst reductive activation cyclic malonyl peroxides, giving access to complex γ-lactones starting from simple olefins. Detailed mechanistic studies were carried out better understand situ formation active catalyst species commercial precursor, well interconversion photocatalytic mechanism γ-lactone products. Specifically, employed broad range tools, including time-resolved spectroscopy, spectroelectrochemistry, transient UV-vis absorption voltammetry, isotopic labeling, radical trapping experiments, NMR density functional theory (DFT) calculations. The synthetic utility this protocol is demonstrated substrate scope study, highlighting facile spirocyclic γ-lactones, widely recognized biological importance.

Язык: Английский

Photoinduced Cobaloxime-Catalyzed Regio- and Diastereoselective Hydrogen-Evolution C(sp3)–H Phosphorylation of Bicyclo[1.1.0]butanes DOI
Pengfei Chen,

Meng-Yuan Dong,

Chun-Yu Han

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 15, 2025

Radical-initiated functionalization of bicyclo[1.1.0]butanes (BCBs) is a straightforward approach to accessing diverse cyclobutane derivatives. However, selective C(sp3)–H at the C2 position BCBs remains scarce. Herein, mild protocol for hydrogen-evolution phosphorylation with enabled by photoinduced cobaloxime catalysis was realized in regio- and diastereoselective manner. This oxidant- additional photocatalyst-free method wide range diarylphosphine oxides. The mechanism studied via control experiments DFT calculation. Moreover, efficiency this highlighted synthesis high-value, structurally complex molecules.

Язык: Английский

Процитировано

0
3-Oxabicyclo[3.1.1]heptanes as Isosteres of meta-Substituted Benzene Rings DOI
Jennifer Morvan, Evelien Renders, Peter Buijnsters

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 20, 2025

Replacement of the aromatic rings in drug candidates with isosteric rigid sp3-rich scaffolds can improve physicochemical properties, increase chance progressing molecule development, and open new chemical space. Isosteres meta-substituted benzenes remain challenging due to difficulty mimicking exit vector angles bond distances. Herein, we report synthesis 1,5-disubstituted 3-oxabicyclo[3.1.1]heptanes (oxa-BCHeps), which serve as saturated isosteres phenyl a similar geometric arrangement. This structural motif be obtained under mild reaction conditions via acid-mediated isomerization (2-oxaspiro[3.3]heptan-6-yl)methanols using catalytic quantities pyridinium chloride (PyrHCl). We demonstrate utility this methodology by preparing various building blocks for use medicinal chemistry incorporating 3-oxa-BCHep into anticancer sonidegib, improving its such permeability, metabolic stability, solubility.

Язык: Английский

Процитировано

0
Phenothiazine Sulfoxides as Active Photocatalysts for the Synthesis of γ-Lactones DOI Creative Commons
Niklas Hölter,

Nils Rendel,

Leander Spierling

и другие.

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

Опубликована: Апрель 2, 2025

N-substituted phenothiazines are prominent and highly effective organic photoredox catalysts, particularly known for their strong reducing capabilities. Despite wide utility, the closely related phenothiazine sulfoxides, which easily form upon oxidation, have been largely overlooked not explored in context of photocatalysis. Herein, we describe discovery application N-phenylphenothiazine sulfoxide as a photocatalyst reductive activation cyclic malonyl peroxides, giving access to complex γ-lactones starting from simple olefins. Detailed mechanistic studies were carried out better understand situ formation active catalyst species commercial precursor, well interconversion photocatalytic mechanism γ-lactone products. Specifically, employed broad range tools, including time-resolved spectroscopy, spectroelectrochemistry, transient UV-vis absorption voltammetry, isotopic labeling, radical trapping experiments, NMR density functional theory (DFT) calculations. The synthetic utility this protocol is demonstrated substrate scope study, highlighting facile spirocyclic γ-lactones, widely recognized biological importance.

Язык: Английский

Процитировано

0