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

Abstract

Employing a CuCl/TMEDA/nor-AZADO catalyst system, various types of structurally diverse imides could be synthesized from various combinations of alcohols and amides.

Recent Advancement in the Copper Mediated Synthesis of Heterocyclic Amides as Important Pharmaceutical and Agrochemicals

“…Furthermore, this work can be extended for the synthesis of α‐ketocarbonyl compounds such as α‐ketoimides, α‐ketoamides, and α‐ketoesters by reacting 1,2‐diols with nucleophiles like amides, amines, and alcohols (See Figure 69). [106] …”

Oxidative Amide Coupling from Functionally Diverse Alcohols and Amines Using Aerobic Copper/Nitroxyl Catalysis

“…The catalyst system favors reaction with the primary amine over the sterically encumbered secondary amine, leading to formation of 26 . The reaction tolerated a primary amide and a free tertiary alcohol ( 30 and 33 ; 89 % and 94 % yields, respectively), showing that this protocol could have advantages over the use of trifluoroacetic anhydride, which can lead to competitive functionalization of other groups in a molecule . Compatible functional groups evident from reactions with the second set of molecules include nitriles, alkenes, nitro groups, imides, cyclopropyl rings, and lactams.…”

“…[14] An initial set of substrates (19)(20)(21)(22)(23)(24)(25)(26)was selected to probe the compatibility of various functional groups,w hile as econd set features an expanded set of functional groups within specific pharmaceutically relevant molecules (27)(28)(29)(30)(31)(32)(33)(34). Functional groups in the first set include oxygen-containing groups (ethers, tBu ester,a nd acetonide [20][21][22], and aromatic heterocycles (thiophene,p yridine,a nd thiazole [23][24][25], all of which formed the desired amide product in very good-to-excellent yields.T he catalyst system favors reaction with the primary amine over the sterically encumbered secondary amine, leading to formation of 26.T he reaction tolerated ap rimary amide [15] and afree tertiary alcohol (30 and 33;89%and 94 % yields,r espectively), showing that this protocol could have advantages over the use of trifluoroacetic anhydride,w hich can lead to competitive functionalization of other groups in am olecule. [16] Compatible functional groups evident from reactions with the second set of molecules include nitriles, alkenes,n itro groups,i mides,c yclopropyl rings,a nd lactams.…”

N-acylation of amides through internal nucleophilic catalysis

“…8 Yamaguchi reported a copper-catalyzed aerobic oxidative acylation of amides with alcohols for the synthesis of imides. 9 Also, Nicolaou reported the oxidation of secondary amides to the corresponding imides using Dess-Martin periodinane. 10 In spite of the above-mentioned methods, imides are usually prepared between amides and an excess of activated forms of carboxylic acids, such as acyl chlorides, anhydrides, and esters, under strong basic or acidic conditions (Scheme 1(a)).…”