The Au(I)-catalysed rearrangement of propargylic esters formed from an ynamide has been studied. The reaction is facile, and when conducted in the presence of a reactive indole nucleophile, leads to a cascade process whereby γ-indolyl α-acyloxyenamides are formed in good yield and excellent E-stereoselectivity.

In this paper, a novel catalyst (MgAl2O4@SiO2-PTA) was proposed for the green oxidation of aliphatic alcohols. The resultant composite was characterized by different techniques, such as X-ray diffraction (XRD), SEM, FT-IR, EDX and Brunauer-Emmett-Teller (BET) surface area analysis. The prepared nanocomposite was used as a catalyst for oxidation of aliphatic alco...

Ring-opening of cyclic sulfamidates with propargylic sulfonamides yielded substrates for a gold-catalyzed cyclization to yield tetrahydropyrazines. Manipulation of the tetrahydropyrazines, by reduction or using multicomponent reactions, yielded piperazine scaffolds in which substitution of the carbon atoms was varied. Such scaffolds may have value in the synthesis of novel screening compounds w...

In the presence of 2-10 mol% of Tf(2)NH, a range of N-benzylic sulfonamides smoothly react with allylic, propargylic, benzylic, or hydrido silanes at room temperature via sp(3) carbon-nitrogen bond cleavage to afford structurally diverse products in moderate to excellent yields and with high chemo- and regioselectivity.

Allenylsilanes reacted at room temperature in acetonitrile with Selectfluor, an electrophilic fluorinating reagent, to give secondary propargylic fluorides in moderate to good yields; mechanistically, a side-product resulting from a 1,2-silyl shift testifies to the presence of a cationic intermediate.

The use of [(IPr)AuOH] permits the generation of gold(i)-amine complexes by a silver-free protocol. These in situ or well-defined complexes are used in a straightforward synthetic route to substituted allenes from propargylic acetates. The catalytic activity can be modulated as a function of the nature of the ligand bound to the gold-NHC moiety.

A titanium-catalyzed cis-hydroalumination of propargylic amines with Red-Al is described, which provides an efficient way to produce Z-configured allylic amines in good to excellent yields with high stereoselectivity and good regioselectivity. The hydride-bridged Al/Ti bimetallic species may act as a real catalyst in this reaction.

An active, recoverable, and recyclable nanocluster catalyst, Au25(SR)18(-), has been developed to catalyze the formation of α,β-unsaturated ketones or aldehydes from propargylic acetates. The catalytic process has been proposed to be initialized by an SN2' addition of OH(-). Moreover, a dramatic solvent effect was observed, for which a rational explanation was provided.

An oxidative amination of allenes using a single hypervalent iodine reagent is reported. The reaction proceeds very efficiently for monosubstituted allenes and leads to formation of the corresponding propargylic amines, either as the internal or as the terminal amine. The respective reaction outcome could be influenced in favor of the former product by addition of triphenylphosphine oxide to th...