On-Surface Synthesis of Helicene Oligomers.

We report on-surface synthesis of heterochiral 1D heptahelicene oligomers after deposition of a racemic heptahelicene monomer on an Au(111) surface followed by Ullmann coupling under ultrahigh vacuum conditions. Structure, chirality and mode of adsorption of the resulting dimers to octamers are inferred from the scanning probe microscopy and theoretical calculations.

Nonaqueous capillary electrophoresis and quantum chemical calculations applied to investigation of acid-base and electromigration properties of azahelicenes.

Nonaqueous capillary electrophoresis (NACE) using methanol (MeOH) as a solvent of the BGEs and quantum mechanical density functional theory (DFT) have been applied to determine the thermodynamic acidity (ionization) constants (pKa ) of mono- and diaza[5]helicenes, mono- and diaza[6]helicenes, and their dibenzo derivatives in MeOH and water. First, the mixed acidity constants, pKa,MeOHmix${\rm{p}}K_{{\rm{a,MeOH}}}^{{\rm{mix}}}$ , of ionogenic pyridinium groups of azahelicenes and their derivatives in MeOH were obtained by nonlinear regression analysis of pH dependence of their effective electrophoretic mobilities. The effective mobilities were measured by NACE in a large series of methanolic BGEs within a wide conventional pH range (pHMeOH 1.6-12.0) and at ambient temperature (21-26°C) in a home-made CE device. Prior to mixed acidity constant calculation, the effective mobilities were corrected to reference temperature (25°C) and constant ionic strength (25 mM). Then, the mixed acidity constants were recalculated to the thermodynamic acidity constants pKa,MeOH by the Debye-Hückel theory of nonideality of electrolyte solutions. Finally, from the methanolic thermodynamic pKa,MeOH values, the aqueous thermodynamic pKa,H2O${\rm{p}}{K_{{\rm{a,}}{{\rm{H}}_{\rm{2}}}{\rm{O}}}}$ constants were estimated using the empirical relations between methanolic and aqueous acidity constants derived for structurally related pyridine derivatives. Depending on the number and position of the nitrogen atoms in their molecules, the analyzed azahelicenes were found to be weak to moderate bases with methanolic pKa,MeOH in the range 2.01-8.75 and with aqueous pKa,H2O${\rm{p}}{K_{{\rm{a,}}{{\rm{H}}_{\rm{2}}}{\rm{O}}}}$ in the range 1.67-8.28. The thermodynamic pKa,MeOH obtained by the DFT calculations were in a good agreement with those determined experimentally by NACE.

Aromatic Azide Transformation on the Ag(111) Surface Studied by Scanning Probe Microscopy.

Chemical transformation of 9-azidophenanthrene on the Ag(111) surface was studied by nc-AFM in UHV. High-resolution imaging supported by first-principle calculations revealed the structure of the final products that originated from a common and elusive 9-phenanthryl nitrenoid intermediate chemisorbed on the Ag(111) surface. A formal nitrene insertion into the C-H bond along with its dimerisation and hydrogenation were identified as main reaction channels. Thus, the ability of aryl azides to form covalent σ- and π-bonds between their transformation products on a solid surface was demonstrated at a single-molecule level.

[2+2+2] Cycloisomerisation of Aromatic Cyanodiynes in the Synthesis of Pyridohelicenes and Their Analogues.

We have developed a methodology for the synthesis of pyridohelicenes and their analogues based on the Ni(0) -, Co(I) - or Rh(I) -mediated intramolecular [2+2+2] cycloisomerisation of cyanodiynes. It allows for folding the linear precursors into the corresponding helical backbones comprising the newly formed pyridine unit in their central part. Along with racemic pyrido[n]helicenes (n=5,6,7) and their derivatives, both enantio- and diastereomerically pure pyrido[n]helicene-like molecules (n=5,6) were prepared by employing the chiral substrate-controlled cyclisation of the corresponding enantiopure cyanodiynes.

The use of cobalt-mediated cycloisomerisation of ynedinitriles in the synthesis of pyridazinohelicenes.

A cobalt-mediated [2+2+2] cycloisomerisation of ynedinitriles to helical pyridazines in good to high yields was developed. The construction of the pyridazine nucleus from one alkyne and two nitrile units is proposed to follow either a conventional organometallic mechanism or to be triggered by a single-electron transfer from a Co(II) species. Various [5]-, [6]- and [7]helicene pyridazines were prepared.

Oxahelicene NHC ligands in the asymmetric synthesis of nonracemic helicenes.

A straightforward approach to enantiopure 2H-pyran-modified amino[5]helicenes and amino[6]helicenes was developed. They were converted to 1,3-disubstituted imidazolium salts and used as NHC ligand precursors in the Ni0-catalysed enantioselective [2+2+2] cycloisomerisation of aromatic triynes to obtain the model helicene derivatives in up to 86% ee.

Azahelicene Superbases as MAILD Matrices for Acidic Analytes.

Fitting the profile: A superbasic 1,14-diaza[5]helicene can serve as an efficient, ionless matrix for matrix-assisted ionization/laser desorption (MAILD) spectrometry. The matrix outperforms other bases by acting as a kinetically active proton sponge and is highly suitable for high-throughput metabolomics analysis. There is a correlation between the basicity (and proton-sponge character) of matrices and their efficacy in MAILD-MS.