The gem-aminoalkynylation of fluorinated diazo compounds catalyzed by a simple Cu(I) salt is described. This three-component reaction allows the synthesis propargylic amines with broad functional group tolerance. Both electron-rich and electron-poor anilines can be used as nucleophiles alkyl-, aryl-, silyl-substituted EthynylBenziodoXoles (EBX) electrophiles.

The direct aldol-type condensation of aldehydes with ethyl diazoacetate catalyzed by the chiral complex of BINOL derivatives-Zr(O(t)Bu)(4) gave beta-hydroxy alpha-diazo carbonyl compounds with moderate enantioselectivities (53-87% ee). [reaction: see text]

Using copper complexes with an axially chiral bipyridine ligand C4-ACBP as the catalyst, an enantioselective functionalization of indoles with diazo compounds was developed with up to 95% ee. This protocol paves the way for further applications of these ligands.

Spiropyrrolidinyloxindole compounds are synthesized in moderate to excellent yield via a highly diastereoselective Cu(I)-catalysed three-component assembly reaction of an imine, diazo-compound and substituted olefin dipolarophile.

Nitrile-substituted cyclopropanes are readily synthesized in a stereocontrolled fashion from the intermolecular cyclopropanation between 2-diazo-2-phenylacetonitrile and electron-rich olefins, catalyzed by the chiral dirhodium complex, Rh(2)(S-PTAD)(4).

One of the difficulties associated with research on ergothioneine has been the lack of completely reliable methods for the quantitative determination of the compound in blood and other tissues. Ergothioneine was originally discovered to be present in the red blood cell by Benedict et al. (1, 2) and by Hunter and Eagles (3, 4), some 25 years ago, because of its reducing action on the arsenophosp...