N-Acetyl Diazocine Derivatives via Cross-Coupling

chemistry Medicinal and pharmaceutical chemistry Nano- and molecular-scale electronics Nano-biomaterials and bioscience Nanomagnetics Nanomaterials, thin films and nanointerfaces Nanomedicine Nanometrology and nanomechanics Nano-optics Nanopatterning, self-assembly and nanofabrication Nanostructures for energy and sensing applications Natural products chemistry Organo main group chemistry Other nanotechnology (unclassified) Other organic chemistry (unclassified) Photochemistry and photovoltaics Physical organic chemistry Supramolecular chemistry Diazocines are photoswitches derived from azobenzenes by bridging the two phenyl rings in ortho position with a CH2CH2 group forming an eight membered (diazocine) ring. Diazocine is superior to most azobenzenes in almost all photophysical properties (switching efficiency, quantum yield, wavelengths etc.). The biggest advantage, especially in photopharmacology and when used in photoswitchable materials, is the inverted thermodynamic stability of the two switching states (isomers). The Z isomer is more stable than the E form. However, one disadvantage that it shares with the frequently used azobenzene is that the switching efficiency decreases sharply with increasing water content in the solvent. In a recently published paper, we reported that replacing one CH2 group in the bridge with NCOCH3 not only confers intrinsic water solubility, but also largely eliminates the problem of reduced switching efficiency in aqueous solutions. In order to investigate the chemistry of this promising photoswitch and to unlock further applications, we now investigate strategies for the synthesis of derivatives, which are based on cross-coupling reactions. 14 vinyl-, aryl-, cyano-, and amino-substituted diazocines were prepared via Stille, Suzuki, and Buchwald-Hartwig reactions. X-ray structures are presented for derivatives 1, 2 and 7.

photoswitch; diazocine; cross-coupling; photoisomerization; N-acetyl diazocine; thermal relaxation | Format: PDF | Size: 9.7 MB | Download | When a peer-reviewed version of this preprint is available, this information will be updated in the information box above. If no peer-reviewed version is available, please cite this preprint using the following information: Brandt, T.; Lentes, P.; Rudtke, J.; Hösgen, M.; Näther, C.; Herges, R. Beilstein Arch. 2024, 202469. doi:10.3762/bxiv.2024.69.v1 Citation data can be downloaded as file using the "Download" button or used for copy/paste from the text window below. Citation data in RIS format can be imported by all major citation management software, including EndNote, ProCite, RefWorks, and Zotero. © 2024 Brandt et al.; licensee Beilstein-Institut. This is an open access work licensed under the terms of the Beilstein-Institut Open Access License Agreement (https://www.beilstein-archives.org/xiv/terms), which is identical to the Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0). The reuse of material under this license requires that the author(s), source and license are credited. Third-party material in this work could be subject to other licenses (typically indicated in the credit line), and in this case, users are required to obtain permission from the license holder to reuse the material.