4.8 Article

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

Journal

ORGANIC LETTERS
Volume 3, Issue 14, Pages 2225-2228

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ol016103j

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Funding

  1. NIGMS NIH HHS [R01 GM039754, GM 39754] Funding Source: Medline

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[GRAPHICS] 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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