Due to the high reactivity of alkoxyl (RO·) radicals and their propensity to easily undergo β-scission or Hydrogen Atom Transfer (HAT) reactions, intermolecular alkoxylations involving RO· radicals are barely described. We report herein for the first time the efficient intermolecular trapping of alkoxyl radicals by silyl enol ethers. This photoredox-mediated protocol enables the introduction of both structurally simple and more complex alkoxy groups into a wide range of ketones and amides.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.orglett.1c03444DOI Listing

Publication Analysis

Top Keywords

alkoxyl radicals
8
ro· radicals
8
intermolecular c-o
4
c-o bond
4
bond formation
4
formation alkoxyl
4
radicals
4
radicals photoredox-catalyzed
4
photoredox-catalyzed α-alkoxylation
4
α-alkoxylation carbonyl
4

Similar Publications

An efficient direct electrolysis method for the synthesis of 1,1,1,3,3,3-hexafluoroisopropyxy substituted imidazo[1,2-]pyridines.

Org Biomol Chem

January 2025

Key Laboratory of Green Chemical Process of Ministry of Education, Hubei Key Laboratory of Novel Chemical Reactor and Green Chemical Technology, School of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430073, P.R. China.

Electrochemical oxidative cross-dehydrogenative-coupling (CDC) is an ideal strategy to conduct the C3-alkoxylation of imidazo[1,2-]pyridine, but it remains a challenge owing to limitation imposed by the use of alkyl alcohols and carboxylic acids. Herein, we report a mild and efficient 2-electrode constant-potential electrolysis of imidazo[1,2-]pyridine with hexafluoroisopropanol (HFIP) to produce various imidazo[1,2-]pyridine HFIP ethers. Mechanistic studies indicated that the electrooxidation reaction might involve radical coupling and ionic reaction.

View Article and Find Full Text PDF

Radical Brook rearrangement: past, present, and future.

Chem Soc Rev

January 2025

The Institute for Advanced Studies, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, Wuhan University, 299 Bayi Road, Wuhan, 430072, China.

The Brook rearrangement has emerged as one of the most pivotal transformations in organic chemistry, with broad applications spanning organic synthesis, drug design, and materials science. Since its discovery in the 1950s, the anion-mediated Brook rearrangement has been extensively studied, laying the groundwork for the development of numerous innovative reactions. In contrast, the radical Brook rearrangement has garnered comparatively less attention, primarily due to the challenges associated with the controlled generation of alkoxyl radicals under mild conditions.

View Article and Find Full Text PDF

This study investigated how methionine (Met) reduced 4-hydroxy-2-nonenal (4-HNE) generation during the heating of soybean oil. The results showed that Met at 5 mM, 10 mM, 15 mM, 20 mM and 30 mM reduced the 4-HNE content by 0.67 %, 58.

View Article and Find Full Text PDF

Unlabelled: Human cytomegalovirus (HCMV) modulates numerous cellular pathways to facilitate infection, including key components in cellular iron homeostasis. Iron is essential to many cellular processes but, if present in excess, drives cell death through ferroptosis. Ferroptosis is a process that is dependent upon the accumulation of oxidatively damaged phospholipids (lipid peroxides); when these lipid peroxides accumulate in membranes, this culminates in plasma membrane rupture and eventual cell lysis.

View Article and Find Full Text PDF

A convenient and efficient transition-metal-free method has been developed for the C(sp)-H alkoxylation/aryloxylation of 1,4-quinones by direct cross-dehydrogenative coupling with readily available alcohols and phenols in the presence of TEMPO under simple and mild conditions. The method allowed the installation of a wide range of alkoxy/aryloxy groups, exhibited high functional group tolerance, showed a broad substrate scope, afforded good to excellent yields of products in a simple one-pot operation, and could be performed on a gram scale. Mechanistic investigation indicated the involvement of the radical pathway.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!