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Cascade Reactions of α‐Phenylcinnamic Acid to Polycyclic Compounds Promoted by High Valent Transition Metal Halides
Author(s) -
Bartalucci Niccolò,
Biancalana Lorenzo,
Bortoluzzi Marco,
Pampaloni Guido,
Giordano Luca,
Zacchini Stefano,
Marchetti Fabio
Publication year - 2018
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201801865
Subject(s) - chemistry , halide , catalysis , chloroform , transition metal , crystal structure , metal , intermolecular force , carboxylic acid , photochemistry , inorganic chemistry , organic chemistry , molecule
Abstract α‐Phenylcinnamic acid converts into polycyclic derivatives by interaction with high valent transition metal halides in chloroform at reflux temperature. Different products, featured by local structural differences depending on the nature of the metal halide system (i. e. WCl 6 , PCl 5 /NbF 5 or PCl 5 /NbCl 5 ), are easily isolable after treatment with water. In particular, WCl 6 configures as an efficient multitasking agent, working as 1) chlorinator of the carboxylic acid function, 2) catalytic precursor for intra‐ and intermolecular rearrangements, and 3) catalytic precursor for Baeyer‐Villiger lactonization in water at ambient temperature, exploiting air as oxidant. The products have been purified by alumina chromatography, and identified by analytical and spectroscopic (IR, NMR) techniques, and by single crystal X‐ray diffraction in three cases. Their formation probably involves a common reaction pathway which has been rationalized by DFT calculations.