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Activation of Benzyl Aryl Carbonates: The Role of Cation-pi Interactions

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dc.contributor.author Reddy, Golipalli Ramana
dc.contributor.author Avadhani, Anusha S.
dc.contributor.author Rajaram, Sridhar
dc.date.accessioned 2017-01-24T06:28:54Z
dc.date.available 2017-01-24T06:28:54Z
dc.date.issued 2016
dc.identifier.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 http://dx.doi.org/10.1021/acs.joc.6b00441 en_US
dc.identifier.citation Journal of Organic Chemistry en_US
dc.identifier.citation 81 en_US
dc.identifier.citation 10 en_US
dc.identifier.issn 0022-3263
dc.identifier.uri https://libjncir.jncasr.ac.in/xmlui/10572/2174
dc.description Restricted Access en_US
dc.description.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. en_US
dc.description.uri http://dx.doi.org/10.1021/acs.joc.6b00441 en_US
dc.language.iso English en_US
dc.publisher American Chemical Society en_US
dc.rights @American Chemical Society, 2016 en_US
dc.subject Chemistry en_US
dc.subject C-Carboxyl Transfer en_US
dc.subject Amino-Aromatic Interactions en_US
dc.subject Acetylcholine-Binding en_US
dc.subject Biomimetic Catalysis en_US
dc.subject Oxazolyl Carbonates en_US
dc.subject Protein Structures en_US
dc.subject Strecker Reactions en_US
dc.subject Aldol Reactions en_US
dc.subject Ammonium-Salts en_US
dc.subject Nitrile Oxides en_US
dc.title Activation of Benzyl Aryl Carbonates: The Role of Cation-pi Interactions en_US
dc.type Article en_US


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