The Steglich Rearrangement of 2‐Oxindole Derivatives Promoted by Anion‐based Nucleophilic Catalysis

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.

Catalyst design within asymmetric organocatalysis

“…In other words, computational modeling has been used as "a tool" to complement experimental investigations and provide understanding. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] Despite this traditional approach, and due to the development of the computational power as well as the balance between both cost and accuracy, computational methods have become an important path for the prediction of catalytic behaviour and, therefore, catalyst design has become a "pot of gold" within the field of computational chemistry. 26,27 For that reason, developing new techniques to improve the accuracy and produce near instantaneous predictions is paramount in present research.…”

“…During the last decade, researchers have used computational chemistry primarily in a supportive role: run chemical experiments first and then appeal to the theoretical approximation to obtain a meaningful correlation between computed and experimentally‐determined structure‐selectivity relationships. In other words, computational modeling has been used as “a tool” to complement experimental investigations and provide understanding 6–25 . Despite this traditional approach, and due to the development of the computational power as well as the balance between both cost and accuracy, computational methods have become an important path for the prediction of catalytic behaviour and, therefore, catalyst design has become a “pot of gold” within the field of computational chemistry 26,27 …”

Meet the Women of Catalysis

“…She has expertise in highly fundamental topics within computational organic chemistry such as asymmetric catalysis, computationally‐led catalysis design, reaction mechanisms and weak interactions from the theoretical perspective. Cristina′s research group works on the area of asymmetric catalysis, with particular focus on the application of computational techniques in the design of organocatalysts as well as prediction and control of catalytic processes, with a direct impact on the development of important pharmaceutical products …”