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dc.contributor.authorReddy, Golipalli Ramana
dc.contributor.authorAvadhani, Anusha S.
dc.contributor.authorRajaram, Sridhar
dc.identifier.citationReddy, 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
dc.identifier.citationJournal of Organic Chemistryen_US
dc.descriptionRestricted Accessen_US
dc.description.abstractBenzyl 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.en_US
dc.publisherAmerican Chemical Societyen_US
dc.rights@American Chemical Society, 2016en_US
dc.subjectC-Carboxyl Transferen_US
dc.subjectAmino-Aromatic Interactionsen_US
dc.subjectBiomimetic Catalysisen_US
dc.subjectOxazolyl Carbonatesen_US
dc.subjectProtein Structuresen_US
dc.subjectStrecker Reactionsen_US
dc.subjectAldol Reactionsen_US
dc.subjectNitrile Oxidesen_US
dc.titleActivation of Benzyl Aryl Carbonates: The Role of Cation-pi Interactionsen_US
Appears in Collections:Research Articles (Sridhar Rajaram)

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