4885-14-7Relevant articles and documents
A palladium-catalyzed C-H functionalization route to ketones: Via the oxidative coupling of arenes with carbon monoxide
Arndtsen, Bruce A.,Kinney, R. Garrison,Levesque, Taleah M.
, p. 3104 - 3109 (2020/03/27)
We describe the development of a new palladium-catalyzed method to generate ketones via the oxidative coupling of two arenes and CO. This transformation is catalyzed by simple palladium salts, and is postulated to proceed via the conversion of arenes into high energy aroyl triflate electrophiles. Exploiting the latter can also allow the synthesis of unsymmetrical ketones from two different arenes.
A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation
Kinney, R. Garrison,Tjutrins, Jevgenijs,Torres, Gerardo M.,Liu, Nina Jiabao,Kulkarni, Omkar,Arndtsen, Bruce A.
, p. 193 - 199 (2018/02/06)
The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.
2-(Trifluoromethylsulfonyloxy)pyridine as a Reagent for the Ketone Synthesis from Carboxylic Acids and Aromatic Hydrocarbons
Keumi, Takashi,Yoshimura, Kiichiro,Shimada, Masakazu,Kitajima, Hidehiko
, p. 455 - 460 (2007/10/02)
A new reagent 2-(trifluoromethylsulfonyloxy)pyridine (TFOP) was prepared by the reaction of sodium salt of 2-pyridinol with trifluoromethylsulfonyl chloride in dioxane.The conpound TFOP in trifluoroacetic acid has been found to intermolecularly dehydrate from benzoic acid and aromatic hydrocarbons to give the corresponding benzophenones in high yield.It was further elucidated, in the reaction of fluorene, that a variety of carboxylic acids can be used as the acyl precursor for the aromatic ketone synthesis in conjunction with the TFOP/TFA system.This acylation procedure has been applied to the synthesis of 2-acylthiophenes, which are hard to prepare in a satisfactory yield by the classical Friedel-Crafts reaction using aluminum chloride as the catalyst.
