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Rhodium‐Catalyzed Annelation of Benzoic Acids with α,β‐Unsaturated Ketones with Cleavage of C−H, CO−OH, and C−C Bonds
Author(s) -
Zhang Guodong,
Hu Zhiyong,
Belitz Florian,
Ou Yang,
Pirkl Nico,
Gooßen Lukas J.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201901309
Subject(s) - chemistry , annulation , carboxylate , medicinal chemistry , ketone , catalysis , benzoic acid , lewis acids and bases , residue (chemistry) , cleavage (geology) , bond cleavage , stereochemistry , rhodium , organic chemistry , geotechnical engineering , fracture (geology) , engineering
Abstract In the presence of a [Cp*RhCl 2 ] 2 catalyst, the Lewis acid In(OTf) 3 , and the mild base Na 2 CO 3 , aromatic carboxylates and α,β‐unsaturated ketones undergo a unique hydroarylation/Claisen/retro‐Claisen process to give the corresponding indanones. In this carboxylate‐directed ortho ‐C−H annelation, the C−COR bond of the ketone and the CO−OH group of the aromatic carboxylate are cleaved, and the hydroxy group is transferred from the aromatic to the aliphatic acyl residue. This reactivity is synthetically useful, particularly when starting from cyclic ketones, which are converted into indanones bearing aliphatic carboxylate side chains, thus greatly increasing the molecular complexity of aromatic carboxylates in a single step.