UNIGE document Scientific Article
previous document  unige:76162  next document
add to browser collection
Title

Selective acceleration of disfavored enolate addition reactions by anion–π interactions

Authors
Published in Chemical Science. 2015, vol. 6, no. 11, p. 6219-6223
Abstract In chemistry and biology, cation–π interactions contribute significantly to many important transformations. In sharp contrast, reactions accomplished with support from the complementary anion–π interactions are essentially unknown. In this report, we show that anion–π interactions can determine the selectivity of the enolate chemistry of malonate half thioesters. Their addition to enolate acceptors is central in natural product biosynthesis but fails without enzymes because non-productive decarboxylation dominates. The newly designed and synthesized anion–π tweezers invert this selectivity by accelerating the disfavored and decelerating the favored process. The discrimination of anionic tautomers of different planarization and charge delocalization on π-acidic surfaces is expected to account for this intriguing “tortoise-and-hare catalysis.” Almost exponentially increasing selectivity with increasing π acidity of the catalyst supports that contributions from anion–π interactions are decisive.
Identifiers
Full text
Structures
Research group Groupe Matile
Citation
(ISO format)
ZHAO, Yingjie et al. Selective acceleration of disfavored enolate addition reactions by anion–π interactions. In: Chemical Science, 2015, vol. 6, n° 11, p. 6219-6223. https://archive-ouverte.unige.ch/unige:76162

230 hits

52 downloads

Update

Deposited on : 2015-10-14

Export document
Format :
Citation style :