B12‐Catalyzed Carbonylation of Carbon Tetrahalides: Using a Broad Range of Visible Light to Access Diverse Carbonyl Compounds DOI Creative Commons
Hisashi Shimakoshi, Keita Shichijo, Miho J. Tanaka

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 1, 2024

Abstract Visible‐light‐driven organic synthesis is a green and sustainable method for producing fine chemicals highly desirable at both laboratory industrial scales. In this study, we developed broad‐range (including the red region) visible‐light‐driven carbonylation of CCl 4 , CBr 3 F with nucleophiles, such as amines alcohols, using B 12 −Mg 2+ /TiO 2 hybrid catalyst. Carbonyl molecules ureas, carbamates, carbonate esters, carbamoyl fluorides were synthesized high selectivity efficiency under mild conditions. Diffuse reflectance UV‐vis spectroscopy, femtosecond time‐resolved diffuse density functional theory calculations revealed reaction mechanism combination S N single‐electron transfer. This rare example low‐energy, red‐light‐driven photocatalysis, which has been desired in recent years. We believe that study provides general platform to access diverse carbonyl could promote photocatalytic reactions on pilot scale.

Язык: Английский

Silver‐Catalyzed Decarboxylative Coupling of Oxamic Acids with Styrenes to Synthesize E‐Cinnamamides: A Distinguish Reaction Pathway DOI Creative Commons

A Ru‐Han,

Yong‐Wang Huo,

Xiao‐Feng Wu

и другие.

ChemistryOpen, Год журнала: 2025, Номер unknown

Опубликована: Янв. 29, 2025

Abstract A silver‐catalyzed decarboxylative coupling of oxamic acids with styrenes has been developed to produce E ‐cinnamamides. Oxamic act as efficient precursors for carbamoy radicals. Based on the mechanistic experiments and intermediate analysis, proposed mechanism involves radical addition styrenes, followed by oxidation solvent participation, ultimately leading formation cinnamamides which is different from reported cases.

Язык: Английский

Процитировано

0

Facile Synthesis of Carbamoyl Fluorides via N-Carbamoylimidazole Activation DOI Creative Commons
A. Meden, Damijan Knez, Stanislav Gobec

и другие.

ACS Omega, Год журнала: 2025, Номер 10(7), С. 6908 - 6917

Опубликована: Фев. 14, 2025

The untapped potential of carbamoyl fluorides for various chemico/biological applications is hampered by the scarcity straightforward and benign methods their synthesis. In this report, we disclose a novel mild three-step procedure that avoids exotic, corrosive, highly toxic reagents. Briefly, commercially available secondary amines are carbamoylated with 1,1′-carbonyldiimidazole, followed alkylation to improve nucleofugality, exchange inorganic KF. This works on gram scale without chromatographic purification. It however limited basic, sterically unhindered alkylation-prone functional groups.

Язык: Английский

Процитировано

0

eFluorination for the Rapid Synthesis of Fluorothioformates from Oxalic Acid Monothioesters DOI

Feba Thomas Pulikkottil,

Marco Galzignato,

Jérémy Saiter

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

An efficient and practical electrochemical method for synthesizing fluorothioformate derivatives, an underexplored functional group, is reported. The strategy based on the anodic decarboxylation of oxalic acid monothioesters, which rapidly generates highly reactive alkyl (oxomethylidene)sulfonium intermediates. These intermediates are effectively trapped by inexpensive commercially available triethylamine trihydrofluoride (Et3N·3HF), acts as both a nucleophilic fluoride source supporting electrolyte, leading to formation desired fluorothioformates. This methodology enables rapid scalable synthesis enabling their broader exploration in organic chemistry. In particular, these compounds can be readily selectively converted S-thiocarbamates urea derivatives one-pot process through reactions with amines, demonstrating synthetic utility. scalability this fluorination was validated, showing no loss yield. Cyclic voltammetry studies were carried out shed some light mechanism novel transformations.

Язык: Английский

Процитировано

0

B12‐Catalyzed Carbonylation of Carbon Tetrahalides: Using a Broad Range of Visible Light to Access Diverse Carbonyl Compounds DOI Creative Commons
Hisashi Shimakoshi, Keita Shichijo, Miho J. Tanaka

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 1, 2024

Abstract Visible‐light‐driven organic synthesis is a green and sustainable method for producing fine chemicals highly desirable at both laboratory industrial scales. In this study, we developed broad‐range (including the red region) visible‐light‐driven carbonylation of CCl 4 , CBr 3 F with nucleophiles, such as amines alcohols, using B 12 −Mg 2+ /TiO 2 hybrid catalyst. Carbonyl molecules ureas, carbamates, carbonate esters, carbamoyl fluorides were synthesized high selectivity efficiency under mild conditions. Diffuse reflectance UV‐vis spectroscopy, femtosecond time‐resolved diffuse density functional theory calculations revealed reaction mechanism combination S N single‐electron transfer. This rare example low‐energy, red‐light‐driven photocatalysis, which has been desired in recent years. We believe that study provides general platform to access diverse carbonyl could promote photocatalytic reactions on pilot scale.

Язык: Английский

Процитировано

0