A two-step approach to achieve secondary amide transamidation enabled by nickel catalysis
نویسندگان
چکیده
A long-standing challenge in synthetic chemistry is the development of the transamidation reaction. This process, which involves the conversion of one amide to another, is typically plagued by unfavourable kinetic and thermodynamic factors. Although some advances have been made with regard to the transamidation of primary amide substrates, secondary amide transamidation has remained elusive. Here we present a simple two-step approach that allows for the elusive overall transformation to take place using non-precious metal catalysis. The methodology proceeds under exceptionally mild reaction conditions and is tolerant of amino-acid-derived nucleophiles. In addition to overcoming the classic problem of secondary amide transamidation, our studies expand the growing repertoire of new transformations mediated by base metal catalysis.
منابع مشابه
Nickel-catalyzed transamidation of aliphatic amide derivatives.
Transamidation, or the conversion of one amide to another, is a long-standing challenge in organic synthesis. Although notable progress has been made in the transamidation of primary amides, the transamidation of secondary amides has remained underdeveloped, especially when considering aliphatic substrates. Herein, we report a two-step approach to achieve the transamidation of secondary aliphat...
متن کاملNickel-catalyzed transamidation of aliphatic amide derivatives† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc01980g
متن کامل
Transamidation reactions catalyzed by cathepsin C.
Previous publications from this laboratory (l-3) have described the catalysis of transamidation reactions by the proteinases papain, ficin, and crystalline chymotrypsin. In addition, preliminary experiments were reported on replacement reactions catalyzed by beef spleen cathepsin C, an intracellular endopeptidase of animal tissues, which resembles pancreatic chymotrypsin in its specificity. The...
متن کاملDiscovery and mechanistic study of Al(III)-catalyzed transamidation of tertiary amides.
Cleavage of the C-N bond of carboxamides generally requires harsh conditions. This study reveals that tris(amido)Al(III) catalysts, such as Al2(NMe2)6, promote facile equilibrium-controlled transamidation of tertiary carboxamides with secondary amines. The mechanism of these reactions was investigated by kinetic, spectroscopic, and density functional theory (DFT) computational methods. The cata...
متن کاملDiaminophosphine oxide ligand enabled asymmetric nickel-catalyzed hydrocarbamoylations of alkenes.
Chiral trivalent phosphorus species are the dominant class of ligands and the key controlling element in asymmetric homogeneous transition-metal catalysis. Here, novel chiral diaminophosphine oxide ligands are described. The arising catalyst system with nickel(0) and trimethylaluminum efficiently activates formamide C-H bonds under mild conditions providing pyrrolidones via intramolecular hydro...
متن کامل