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The Steglich Rearrangement of 2‐Oxindole Derivatives Promoted by Anion‐based Nucleophilic Catalysis
Author(s) -
Trujillo Cristina,
Litvajova Mili,
Cronin Sarah A.,
Craig Ryan,
Con Stephen J.
Publication year - 2019
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201900756
Subject(s) - chemistry , nucleophile , oxindole , fluoride , catalysis , medicinal chemistry , reaction mechanism , cyanide , organic chemistry , inorganic chemistry
The first small anion‐triggered Steglich rearrangements are reported. Tetrabutylammonium carboxylates‐, cyanide‐ and fluoride promote the O ‐ to C ‐acyl transfer of a range of O‐acylated oxindoles to form 3,3‐disubstituted oxindole products with new quaternary stereocentres. DFT calculations on the TBAF‐mediated reaction strongly support a nucleophilic catalysis mechanism involving initial attack of fluoride on the O ‐acyl group to give an enolate and an acyl fluoride in the rate determining step.