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Relevant academic research and scientific papers

CuCl/TMEDA/nor-AZADO-catalyzed aerobic oxidative acylation of amides with alcohols to produce imides

Although aerobic oxidative acylation of amides with alcohols would be a good complement to classical synthetic methods for imides (e.g., acylation of amides with activated forms of carboxylic acids), to date, there have been no reports on oxidative acylation to produce imides. In this study, we successfully developed, for the first time, an efficient method for the synthesis of imides through aerobic oxidative acylation of amides with alcohols by employing a CuCl/TMEDA/nor-AZADO catalyst system (TMEDA = teramethylethylendiamine; nor-AZADO = 9-azanoradamantane N-oxyl). The proposed acylation proceeds through the following sequential reactions: aerobic oxidation of alcohols to aldehydes, nucleophilic addition of amides to the aldehydes to form hemiamidal intermediates, and aerobic oxidation of the hemiamidal intermediates to give the corresponding imides. This catalytic system utilizes O2 as the terminal oxidant and produces water as the sole by-product. An important point for realizing this efficient acylation system is the utilization of a TMEDA ligand, which, to the best of our knowledge, has not been employed in previously reported Cu/ligand/N-oxyl systems. Based on experimental evidence, we consider that plausible roles of TMEDA involve the promotion of both hemiamidal oxidation and regeneration of an active CuII-OH species from a CuI species. Here promotion of hemiamidal oxidation is particularly important. Employing the proposed system, various types of structurally diverse imides could be synthesized from various combinations of alcohols and amides, and gram-scale acylation was also successful. In addition, the proposed system was further applicable to the synthesis of α-ketocarbonyl compounds (i.e., α-ketoimides, α-ketoamides, and α-ketoesters) from 1,2-diols and nucleophiles (i.e., amides, amines, and alcohols).

Chemoselective acylation of primary amines and amides with potassium acyltrifluoroborates under acidic conditions

Current methods for constructing amide bonds join amines and carboxylic acids by dehydrative couplings-processes that usually require organic solvents, expensive and often dangerous coupling reagents, and masking other functional groups. Here we describe an amide formation using primary amines and potassium acyltrifluoroborates promoted by simple chlorinating agents that proceeds rapidly in water. The reaction is fast at acidic pH and tolerates alcohols, carboxylic acids, and even secondary amines in the substrates. It is applicable to the functionalization of primary amides, sulfonamides, and other N-functional groups that typically resist classical acylations and can be applied to late-stage functionalizations.

Copper-catalyzed synthesis of imides from aldehydes or alcohols and amine hydrochloride salts

An efficient approach to imides has been developed. With tert-butyl hydroperoxide (TBHP) as the oxidant, CuBr (20 mol-%) as the catalyst, and PhI(OAc)2 (50 mol-%) as the additive, aldehydes or alcohols reacted with amine hydrochloride salts to provide imides in moderate to good yields. A possible reaction pathway for the formation of the products is also discussed in this paper.

Palladium-catalyzed aminocarbonylation of aryl iodides with amides and N-alkyl anilines

A novel and efficient palladium-catalyzed aminocarbonylation of aryl iodides with amides and N-alkyl anilines has been developed. The reaction tolerates a wide range of functional groups and is a reliable method for the rapid synthesis of a variety of valuable imides and tertiary benzanilides under an atmospheric pressure of CO. Copyright

Highly efficient iron(II) chloride/N-bromosuccinimide-mediated synthesis of imides and acylsulfonamides

We have developed a general and highly efficient iron(II) chloride/N-bromosuccinimide (NBS)-mediated method for the synthesis of imides and acylsulfonamides via couplings of thioesters with carboxamides/sulfonamides, and the method is simple, economical and shows practical advantages.