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What is the stabilizing interaction with nucleophilic solvents in the transition state for solvolysis of tertiary derivatives: nucleophilic solvent participation or nucleophilic solvation?



What is the stabilizing interaction with nucleophilic solvents in the transition state for solvolysis of tertiary derivatives: nucleophilic solvent participation or nucleophilic solvation?



Organic Letters 3(14): 2225-2228



[structure: see text] We propose that controversy concerning the mechanism for solvolysis at tertiary carbon is semantic and can be avoided by making a clear distinction between (1) nucleophilic solvent participation, which is stabilization of the transition state for concerted solvolysis by formation of a partial covalent bond to the solvent nucleophile, and (2) nucleophilic solvation, which is stabilization of the transition state for stepwise solvolysis through carbocation or ion pair intermediates by charge-dipole interactions with nucleophilic solvents.

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Accession: 047959426

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PMID: 11440585

DOI: 10.1021/ol016103j


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