TY - JOUR
T1 - Oxidative Approach Enables Efficient Access to Cyclic Azobenzenes
AU - Maier, Martin S.
AU - Hüll, Katharina
AU - Reynders, Martin
AU - Matsuura, Bryan S.
AU - Leippe, Philipp
AU - Ko, Tongil
AU - Schäffer, Lukas
AU - Trauner, Dirk
N1 - Funding Information:
K.H. thanks the Studienstiftung des deutschen Volkes for a Ph.D. scholarship. B.S.M. thanks the Alexander von Humboldt Foundation for a postdoctoral research fellowship. D.T. was supported by the European Research Council (Advanced Grant 268795) and thanks go to the Centre for Integrated Protein Science Munich (CIPSM). M.R. and D.T. thank the German Research Foundation (DFG) for financial support (SFB749). We further acknowledge National Institutes of Health (NIH) support (OD016343). T.K. thanks New York University for a MacCracken fellowship. The Shared Instrumentation Facility at the New York University Department of Chemistry was supported by a NIH Research Facilities Improvement Award (C06 RR-16572-01) and a NIH S10 grant (OD016343). The authors thank Dr. Chin Lin for his assistance with NMR spectroscopy and mass spectrometry and Christopher Arp for programming the MATLAB interface to control the monochromator.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/10/30
Y1 - 2019/10/30
N2 - Azobenzenes are versatile photoswitches that have found widespread use in a variety of fields, ranging from photopharmacology to the material sciences. In addition to regular azobenzenes, the cyclic diazocines have recently emerged. Although diazocines have fascinating conformational and photophysical properties, their use has been limited by their synthetic accessibility. Herein, we present a general, high-yielding protocol that relies on the oxidative cyclization of dianilines. In combination with a modular substrate synthesis, it allows for rapid access to diversely functionalized diazocines on gram scales. Our work systematically explores substituent effects on the photoisomerization and thermal relaxation of diazocines. It will enable their incorporation into a wide variety of functional molecules, unlocking the full potential of these emerging photoswitches. The method can be applied to the synthesis of a new cyclic azobenzene with a nine-membered central ring and distinct properties.
AB - Azobenzenes are versatile photoswitches that have found widespread use in a variety of fields, ranging from photopharmacology to the material sciences. In addition to regular azobenzenes, the cyclic diazocines have recently emerged. Although diazocines have fascinating conformational and photophysical properties, their use has been limited by their synthetic accessibility. Herein, we present a general, high-yielding protocol that relies on the oxidative cyclization of dianilines. In combination with a modular substrate synthesis, it allows for rapid access to diversely functionalized diazocines on gram scales. Our work systematically explores substituent effects on the photoisomerization and thermal relaxation of diazocines. It will enable their incorporation into a wide variety of functional molecules, unlocking the full potential of these emerging photoswitches. The method can be applied to the synthesis of a new cyclic azobenzene with a nine-membered central ring and distinct properties.
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U2 - 10.1021/jacs.9b08794
DO - 10.1021/jacs.9b08794
M3 - Article
C2 - 31584272
AN - SCOPUS:85073829363
SN - 0002-7863
VL - 141
SP - 17295
EP - 17304
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 43
ER -