A variety of functionalities, including the whole range of halogen substituents, are tolerated in the title reaction, an intramolecular approach for the construction of a multisubstituted indole skeleton from readily available enaminones (see scheme; phen=1,10‐phenanthroline). The indole products are also prepared directly in high yield from α,β‐ynones and primary amines.

The mesoscopic morphology of binary mixtures of ethylammonium nitrate (EAN), the protic ionic liquid par excellence, and methanol is explored using neutron/X-ray diffraction and computational techniques. Both compounds are amphiphilic and characterized by an extended hydrogen bonding network: surprisingly, though macroscopically homogeneous, these mixtures turn out to be mesoscopically highly heterogeneous. Our study reveals that even in methanol-rich mixtures, a wide distribution of clusters exists where EAN preserves its bulk, sponge-like morphology. Accordingly methanol does not succeed in fully dissociating the ionic liquid that keeps on organizing in a bulk-like fashion. This behavior represents the premises to the more dramatic phenomenology observed with longer alcohols that eventually phase separate from EAN. These results challenge the commonly accepted polar and apolar moieties segregation in ionic liquids/molecular liquids mixtures and the current understanding of technologically relevant solvation processes.

We present an analysis of the liquid and of a small isolated cluster of n-ethyl ammonium nitrate based on "first principles" molecular dynamics. We discover that the peculiar properties of ionic liquids make such compounds ideal candidates for such an analysis. We have been able to characterize some important features of the liquid structure and we have validated our simulations by comparing our findings with experimental vibrational spectra of the liquid phase. Theoretical spectra, which present a remarkable agreement with the measurements, besides the assignment of the main spectra features, allow an interpretation of the spectra at high frequencies where the vibrational motions involve the hydrogen-bonded atoms, thus providing a picture of the hydrogen bonding network that exists in such compounds.

An efficient cross-coupling of terminal alkynes with arenediazonium salts has been developed. To the best of our knowledge, this transformation is the first example of the alkynylation of arenediazonium salts. The reaction occurs under mild conditions in the presence of nBu4NI and proceeds through a domino iododediazoniation/Sonogashira cross-coupling sequence. Good to excellent yields are usually obtained. A variety of alkyl, aryl, and heteroaryl substituentson the alkyne substrate can be used and many useful functionalities including bromo, chloro, keto, ester, ether, cyano, and nitro substituents on the arenediazonium salt are also tolerated. ortho Substituents, both in the arenediazonium salt and the alkynylarene, are also tolerated. The formation of alkynylarenes bearing 2-chloro-, 2-bromo-, 2-amino-, and 2- hydroxyaryl moieties may be exceedingly useful for appending heterocyclic rings to aniline fragments. The entire arenediazonium salt synthesis/iododediazoniation/cross-coupling sequence can also be performed as a one-pot domino process, omitting the isolation of the arenediazonium salt

A novel palladium-catalyzed synthesis of free N-H 2,3-disubstituted indoles from arenediazonium tetrafluoroborates and 2-alkynyltrifluoroacetanilides is presented. The reaction tolerates a variety of useful substituents both in the starting alkyne and the arenediazonium salt, including bromo and chloro substituents, nitro, cyano, keto, ester, and ether groups, as well as ortho substituents such as methoxy and methyl groups.