NDLI: Dynamic Effects Dictate the Mechanism and Selectivity of Dehydration–Rearrangement Reactions of Protonated Alcohols $[Me_{2}(R)CCH(OH_{2})Me]^{+}$ (R=Me, Et, iPr) in the Gas Phase

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Dynamic Effects Dictate the Mechanism and Selectivity of Dehydration–Rearrangement Reactions of Protonated Alcohols $[Me_{2}(R)CCH(OH_{2})Me]^{+}$ (R=Me, Et, iPr) in the Gas Phase

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Dynamic Effects Dictate the Mechanism and Selectivity of Dehydration–Rearrangement Reactions of Protonated Alcohols $[Me_{2}(R)CCH(OH_{2})Me]^{+}$ (R=Me, Et, iPr) in the Gas Phase

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Ventura, Elizete Do Monte, Silmar A. De Souza, Miguel A. F. Longo, Ricardo L. Riveros, José M.
Description	Author Affiliation: de Souza MA ( Departamento de Química Fundamental, Universidade Federal de Pernambuco, 50.740-560, Recife, PE (Brazil), Fax:(+55) 83-21268000)
Abstract	The gas-phase dehydration–rearrangement (DR) reactions of protonated alcohols $[Me_{2}(R)CCH(OH_{2})Me]^{+}$ [R=Me (ME), Et (ET), and iPr (I-PR)] were studied by using static approaches (intrinsic reaction coordinate (IRC), Rice–Ramsperger–Kassel–Marcus theory) and dynamics (quasiclassical trajectory) simulations at the B3LYP/6-31G(d) level of theory. The concerted mechanism involves simultaneous water dissociation and alkyl migration, whereas in the stepwise reaction pathway the dehydration step leads to a secondary carbocation intermediate followed by alkyl migration. Internal rotation (IR) can change the relative position of the migrating alkyl group and the leaving group (water), so distinct products may be obtained: $[Me(R)CCH(Me)Me⋅⋅⋅OH_{2}]^{+}$ and $[Me(Me)CCH(R)Me⋅⋅⋅OH_{2}]^{+}.$ The static approach predicts that these reactions are concerted, with the selectivity towards these different products determined by the proportion of the conformers of the initial protonated alcohols. These selectivities are explained by the DR processes being much faster than IR. These results are in direct contradiction with the dynamics simulations, which indicate a predominantly stepwise mechanism and selectivities that depend on the alkyl groups and dynamics effects. Indeed, despite the lifetimes of the secondary carbocations being short (<0.5 ps), IR can take place and thus provide a rich selectivity. These different selectivities, particularly for ET and I-PR, are amenable to experimental observation and provide evidence for the minor role played by potential-energy surface and the relevance of the dynamics effects (non-IRC pathways, IR) in determining the reaction mechanisms and product distribution (selectivity).
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	42
Volume Number	20
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2014-10-13
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Alcohols Chemistry Alkylation Gases Molecular Dynamics Simulation Protons Quantum Theory Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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