@article{85498d3096c247a58a62dc471df07381,
title = "Bioinspired Synthesis of (−)-PF-1018",
abstract = "The combination of electrocyclizations and cycloadditions accounts for the formation of a range of fascinating natural products. Cascades consisting of 8π electrocyclizations followed by a 6π electrocyclization and a cycloaddition are relatively common. We now report the synthesis of the tetramic acid PF-1018 through an 8π electrocyclization, the product of which is immediately intercepted by a Diels–Alder cycloaddition. The success of this pericyclic cascade was critically dependent on the substitution pattern of the starting polyene and could be rationalized through DFT calculations. The completion of the synthesis required the instalment of a trisubstituted double bond by radical deoxygenation. An unexpected side product formed through 4-exo-trig radical cyclization could be recycled through an unprecedented triflation/fragmentation.",
keywords = "Diels–Alder cycloaddition, biomimetic synthesis, electrocyclization, tetramic acids, total synthesis",
author = "Hugo Quintela-Varela and Jamieson, {Cooper S.} and Qianzhen Shao and Houk, {K. N.} and Dirk Trauner",
note = "Funding Information: We thank Petr Tatarskiy for his synthesis work, Dr. Peter Mayer (LMU) and Prof. Chunhua Hu (NYU) for X‐ray structure analysis, and Dr. Chin Lin for assistance with NMR measurements. The TCI cryoprobe used for NMR acquisition was supported by the National Institutes of Health (OD016343). We would also like to thank the National Science Foundation (NSF CHE‐1806581 to K.N.H.) for funding. All computational resources were provided by the Institute for Digital Research and Education. C.S.J. is supported by generous funding through the Saul Winstein Fellowship. Funding Information: We thank Petr Tatarskiy for his synthesis work, Dr. Peter Mayer (LMU) and Prof. Chunhua Hu (NYU) for X-ray structure analysis, and Dr. Chin Lin for assistance with NMR measurements. The TCI cryoprobe used for NMR acquisition was supported by the National Institutes of Health (OD016343). We would also like to thank the National Science Foundation (NSF CHE-1806581 to K.N.H.) for funding. All computational resources were provided by the Institute for Digital Research and Education. C.S.J. is supported by generous funding through the Saul Winstein Fellowship. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",
year = "2020",
month = mar,
day = "23",
doi = "10.1002/anie.201912452",
language = "English (US)",
volume = "59",
pages = "5263--5267",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "13",
}