17894-26-7Relevant academic research and scientific papers
Synthesis, structural investigations, hydrogen-deuterium exchange studies, and molecular modeling of conformationally stablilized aromatic oligoamides
Yan, Yan,Qin, Bo,Ren, Changliang,Yip, Yeow Kwan,Ye, Ruijuan,Zeng, Huaqiang,Chen, Xiuying,Su, Haibin,Zhang, Dawei
supporting information; experimental part, p. 5869 - 5879 (2010/07/13)
Biasing the conformational preferences of aromatic oligoamides by internally placing intramolecular hydrogen bonds has led to a series of stably folded molecular strands. This article presents the results from extensive solid-state, solution, and computational studies on these folding oligomers. Depending on its backbone length, an oligoamide adopts a crescent or helical conformation. Surprisingly, despite the highly repetitive nature of the backbone, the internally placed, otherwise very similar intramolecular hydrogen bonds showed significantly different stabilities as demonstrated by hydrogen-deuterium exchange data. It was also observed that the hydrogen-bonding strength can be tuned by adjusting the substituents attached to the exterior of the aromatic backbones. Examining the amide hydrogen-deuterium exchange rates of trimers revealed that a six-membered hydrogen bond nearing the ester end is the weakest among all the four intramolecular hydrogen bonds of a molecule. This observation was verified by ab initio quantum mechanical calculations at the level of B3LYP/6-31G. Such a "weak point" creates the "battle of the bulge" where backbone twisting is centered, which is consistently observed in the solid-state structures of the four trimer molecules studied. In the solid state, the oligomers assemble into interesting one-dimensional structures. A pronounced columnar packing of short oligomers (i.e., dimers, trimers, and tetramer) and channel-like, potentially ion-conducting stacks of longer oligomers (i.e., tetramer, pentamer, and hexamer) were observed.
Synthesis of a pyrrolo[1,4]benzodiazepinequinone
Tapia, Ricardo A.,Centella, Cesar R.,Valderrama, Jaime A.
, p. 2163 - 2168 (2007/10/03)
Condensation of 3,6-dimethoxy-2-nitrobenzoyl chloride with L-proline methyl ester afforded amide 4, which underwent reductive cyclization with iron(II) sulfate and ammonium hydroxide to yield pyrrolobenzodiazepine 5. Oxidation of 5 with ammonium cerium(IV
