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Title: Activation of Benzyl Aryl Carbonates: The Role of Cation-pi Interactions
Authors: Reddy, Golipalli Ramana
Avadhani, Anusha S.
Rajaram, Sridhar
Keywords: Chemistry
C-Carboxyl Transfer
Amino-Aromatic Interactions
Biomimetic Catalysis
Oxazolyl Carbonates
Protein Structures
Strecker Reactions
Aldol Reactions
Nitrile Oxides
Issue Date: 2016
Publisher: American Chemical Society
Citation: Reddy, G. R.; Avadhani, A. S.; Rajaram, S., Activation of Benzyl Aryl Carbonates: The Role of Cation-pi Interactions. Journal of Organic Chemistry 2016, 81 (10), 4134-4141
Journal of Organic Chemistry
Abstract: Benzyl aryl carbonates can react with a nucleophile to yield an activated electrophile and an aryloxide anion. Previously, we had utilized this in the synthesis of alpha-nitro esters from nitroalkanes. To further understand the process of activation of these carbonates by nucleophiles, we have performed kinetic studies on the hydrolysis of carbonates using nucleophiles. Rate constants for the hydrolysis were obtained under pseudo-first-order conditions with DABCO as the nucleophile. A comparison of rate constant for hydrolysis of isobutyl phenyl carbonate with benzyl phenyl carbonate shows that the presence of benzyl group results in a 16-fold acceleration of hydrolysis rate. This indicates that the transition state for activation of carbonate is stabilized by cation-pi interactions. A comparison of the rate constant for various aromatic rings indicates that electron-donating substituents on the benzyl groups accelerate the rate of hydrolysis. Studies were also carried out with DMAP as nucleophile and the results are presented. Our studies show that stable carbonates can be activated using nucleophiles. Activated acyl groups generated from acid anhydrides have been used in several enantioselective reactions. Our studies show that carbonates can be stable alternatives to acid anhydrides.
Description: Restricted Access
ISSN: 0022-3263
Appears in Collections:Research Articles (Sridhar Rajaram)

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