Regioselective Synthesis of Multifunctional Allylic Amines; Access to Ambiphilic Aziridine Scaffolds

Hydroamination of terminal alkynes with secondary amines catalyzed by copper: regioselective access to amines.

A simple and convenient copper-catalyzed hydroamination of arylacetylenes with secondary amines has been performed giving a simple access to aliphatic amines after reduction of the hydroaminated products (E-enamines). Here we described a mild catalytic system utilizing CuCN precatalyst without any additive ligands in a solvent-free system.

Asymmetric Enzymatic Synthesis of Allylic Amines: A Sigmatropic Rearrangement Strategy.

Sigmatropic rearrangements, while rare in biology, offer opportunities for the efficient and selective synthesis of complex chemical motifs. A "P411" serine-ligated variant of cytochrome P450(BM3) has been engineered to initiate a sulfimidation/[2,3]-sigmatropic rearrangement sequence in whole E. coli cells, a non-natural function for any enzyme, providing access to enantioenriched, protected a...

Regioselective Rhodium-Catalyzed Allylic Amination

A metagenomics approach for new biocatalyst discovery: application to transaminases and the synthesis of allylic amines†

Transaminase enzymes have significant potential for the sustainable synthesis of amines using mild aqueous reaction conditions. Here a metagenomics mining strategy has been used for new transaminase enzyme discovery. Starting from oral cavity microbiome samples, DNA sequencing and bioinformatics analyses were performed. Subsequent in silico mining of a library of contiguous reads built from the...

Ambiphilic allenes: synthesis and reactivity.

Ambiphilic allenes are generated by an organocatalyzed domino reaction of alkyl propiolates and aromatic 1,2-diketones; in the absence of any external chemical agent, these allenes perform a thermally-driven dimerization reaction to generate the corresponding fully-substituted cyclobutanes in a regio- and highly stereoselective manner.