We herein describe a simple and metal-free domino methodology to synthesize 2-aminopyrroles from alkynyl vinyl hydrazides. The reaction involves novel propargylic 3,4-diaza-Cope rearrangement tandem isomerization/5-exo-dig N-cyclization reaction. By using this approach, number of with diverse substituents have been prepared.

Cu(I)-catalyzed anti-S(N)2'-type reduction of internal propargylic carbonates with hydrosilanes affords various di- and trisubstituted allenes with high regioselectivities; the reactions are compatible with functional groups and work efficiently for the synthesis of optically-active allenes.

Mono- and 1,3-disubstituted allenes were synthesized from the corresponding propargylamines via palladium-catalysed hydride-transfer reaction. In the current transformation, propargylic amines can be handled as allenyl anion equivalents and introduced into various electrophiles to be transformed into allenes under palladium-catalyzed conditions.

We discovered a 1,3-dipolar species co-existing in two different structures. Photolysis of matrix-isolated 5-phenyltetrazole generates two forms of phenylnitrile imine: propargylic and allenic. They are not resonance structures but correspond to different energy minima, representing bond-shift isomers. These distinct species were characterized spectroscopically and confirmed by calculations up ...

Aryl free-radicals generated at the C-7 position of ethyl indole-2-carboxylates bearing N-allyl and propargylic groups triggered intramolecular cyclizations to furnish a new class of Duocarmycin analogues, formal ethyl pyrrolo[3,2,1-ij]quinoline-2- carboxylate derivatives, through the less favorable 6-endo-trig cyclization mode.

Synthesis of a 9-membered azaenediyne has been achieved for the first time via intramolecular N-alkylation; the importance of proximity of the reacting centres via cobalt carbonyl complexation of the acetylenic moiety and not the activation of propargylic carbon has been demonstrated.

The allene-diyne natural product nemotin was synthesized for the first time through an enantioselective route with the stereogenic center at the lactone moiety derived from l-glutamic acid and the allene axis constructed from the corresponding propargylic tosylate, and the absolute configuration was thus established as (4S,5aS).

dodecylbenzenesulfonic acid (dbsa) was used as an efficient, cheap and stable brønsted catalyst for acetylation of alcohols and phenols and formylation of alcohols under solvent-free conditions. various primary, secondary and tertiary alcohols were acetylated with acetic anhydride as an acetylating agent under solvent-free conditions in the presence of catalytic amount of dbsa at room temperatu...

A highly enantioselective and diastereoselective copper(II)-bisoxazolidine catalyzed nitroaldol reaction with aliphatic and aromatic trifluoromethyl ketones is described.