A series of 5,7,9-substituted 2-azapyrenes were synthesized for the first time. The synthesis relies on Brønsted acid promoted benzannulation of alkyne precursors prepared by palladium-catalyzed cross-coupling reactions. The synthetic strategy is efficient and the scope covers a variety of functional groups. The electrochemical behavior and photophysical properties of the products were investigated by UV−vis and fluorescence spectroscopy, cyclic voltammetry, and DFT calculations.

A series of hitherto unknown 5,14‐diphenylbenzo[j]naphtho[2,1,8‐def][2,7]phenanthrolines, containing a 5‐azatetracene and a 2‐azapyrene subunit, were prepared by combination of Pd‐catalyzed cross‐coupling reactions with a one‐pot Povarov/cycloisomerization reaction. In the final key step four new bonds are formed in one step. The synthetic approach allows for a high degree of diversification of the heterocyclic core structure. The optical and electrochemical properties were studied experimentally and by DFT/TD‐DFT and NICS calculations. Due to the presence of the 2‐azapyrene subunit, the typical electronic nature and characteristics of the 5‐azatetracene moiety are lost and the compounds are electronically and optically more related to 2‐azapyrenes.

The total synthesis of a new dabigatran derivative featuring a tosyl protecting group at the amidine group of dabigatran was explored. During the course of this work, different new synthetic pathways towards dabigatran intermediates are investigated and known concepts revisited. In this context, it was found that, in our hands, a published synthesis did not work as reported. Part of the synthetic strategy presented herein is an amidine‐selective tosylation of 4‐aminobenzamidine. Furthermore, two new dabigatran derivatives exhibit thrombin inhibition activity.

Two new and efficient methods for the synthesis of benzo[b]carbazolediones have been developed. Various derivatives were synthesized by either a three‐component one‐pot reaction or a two‐component domino reaction in moderate to good yield. Moreover, inhibition studies of these compounds against nucleotide pyrophosphatases (NPPs) have been carried out. An interesting and promising inhibitory effect was observed by the influence of different substituents. Substitution with a methyl group located at the indole moiety was found sensitive towards h‐NPP1 (4b; IC50 ±SEM = 0.57 ± 0.05 μM), while the unsubstituted derivative exhibited a higher sensitivity towards h‐NPP3 (4a; IC50 ± SEM = 0.16 ± 0.06 μM). Both derivatives presented non‐selective inhibition of both isozymes. Among all the derivatives, two derivatives with anisyl groups showed the highest selectivity towards h‐NPP3 and no interaction with h‐NPP1. Finally, the free binding energies were calculated and molecular docking studies were performed in order to provide an insight into putative binding modes of these inhibitors.