An Unusual Rearrangement of Pyrazole Nitrene and Coarctate Ring-Opening/Recyclization Cascade: Formal CH-Acetoxylation and Azide/Amine Conversion without External Oxidants and Reductants.

We report an unusual transformation where the transient formation of a nitrene moiety initiates a sequence of steps leading to remote oxidative C-H functionalization (R-CH3 to R-CH2OC(O)R') and the concomitant reduction of the nitrene into an amino group. No external oxidants or reductants are needed for this formal molecular comproportionation. Detected and isolated intermediates and computational analysis suggest that the process occurs with pyrazole ring opening and recyclization.

The synthesis and crystal structure of pH-sensitive fluorescent pyrene-based double aza- and diaza[4]helicenes.

Novel pyrene-based double aza- and diaza[4]helicenes have been prepared through a five-step synthetic sequence in overall good yields. Commercially available 2,3-dihaloazines (2,3-dibromopyridine, 2,3-dichloropyrazine and 2,3-dichloroquinoxaline) were used as starting materials. The synthesis employs electrophile-induced cyclizations of ortho-alkynyl bihetaryls as the key steps, leading to the formation of a helical skeleton. To discern the effect of merging azine and pyrene moieties within a helical skeleton, the X-ray structures, UV-vis absorption and fluorescence spectra of the helicenes were investigated and compared with those of the parent [4]helicene, aza- and diaza[4]helicenes. It was found that the emission properties of the synthesized helicenes can be modulated as a function of pH. The basicity of pyrene-based double aza[4]helicenes was estimated by the direct fluorimetric titration method; the pKa value was found to be equal to 1.4.

Synthesis, crystal structures and properties of carbazole-based [6]helicenes fused with an azine ring.

Novel carbazole-based [6]helicenes fused with an azine ring (pyridine, pyrazine or quinoxaline) have been prepared through a five-step synthetic sequence in good overall yields. Commercially available 2,3-dihaloazines were used as starting materials. To discern the effect of merging an azine moiety within a helical skeleton, the X-ray structures, UV-vis absorption and fluorescence spectra of the helicenes were investigated and compared to that of the parent carbazole-based [6]helicene (7H-phenanthro[3,4-c]carbazole).