A novel-type luciferin from Siberian luminous earthworm Fridericia heliota : structure elucidation by spectral studies and total synthesis

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of Wiley-VCH Verlag GmbH & Co for personal use, not for redistribution. The definitive version was published in Angewandte Chemie International Edition 53 (2014): 5566–5568, doi:10.1002/anie.201400529.We report structure elucidation and synthesis of the luciferin from the recently discovered luminous earthworm Fridericia heliota. This luciferin represents a key component of a novel ATP-dependent bioluminescence system. The UV, fluorescence, NMR and HRMS spectral studies were performed on 5 mkg of the isolated substance, and gave four isomeric structures, conforming with spectral data. These isomers were chemically synthesized and one of them was found to produce light in the reaction with a protein extract from Fridericia. The novel luciferin was found to have an unusual deeply modified peptidic nature, implying an unprecedented mechanism of action.We acknowledge support from the Program of the Government of the Russian Federation “Measures to attract leading scientists to Russian educational institutions” (grant no. 11. G34.31.0058), the programs MCB RAS, President of the Russian Federation “Leading science school” (grant 3951.2012.4) and the Russian Foundation for Basic Research (grant 14-03-01015). B.M.S. was supported by a stipend from the Program of the President of the Russian Federation.2015-04-1

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