The Steglich Rearrangement of 2‐Oxindole Derivatives Promoted by Anion‐based Nucleophilic Catalysis. Issue 16 (17th June 2019)

• Record Type: Journal Article
• Authors: Trujillo, Cristina; Litvajova, Mili; Cronin, Sarah A.; Craig, Ryan; Connon, Stephen J.
• Is Part Of: ChemCatChem. Volume 11:Issue 16(2019)
• Page Start: 3776
• Page End: 3780
• Publication Date: 2019-06-17
• Subjects: Fluoride -- Oxindoles -- Steglich rearrangement -- Catalysis -- DFT; Catalysis -- Periodicals; 541.39505
• DOI: 10.1002/cctc.201900756
• Languages: English
• ISSNs: 1867-3880

Abstract

Abstract: 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. Abstract : Small but mighty : An experimental and computational DFT study has shown that O ‐ to C ‐acyl transfer in 2‐oxindole derivatives is promoted by fluoride via a nucleophilic catalysis mechanism.Ruble, G. C. Fu, J. Am. Chem. Soc ., 1998, 120, 11532.