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Quantum chemical characterization of cycloaddition reactions between 1,3‐butadiene and oxyallyl cations of varying electrophilicity †
Author(s) -
Cramer Christopher J.,
Barrows Susan E.
Publication year - 2000
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(200003)13:3<176::aid-poc232>3.0.co;2-v
Subject(s) - chemistry , cycloaddition , electrophile , concerted reaction , computational chemistry , lithium (medication) , ring (chemistry) , claisen rearrangement , medicinal chemistry , organic chemistry , catalysis , medicine , endocrinology
Hydroxyallyl cation and lithium and sodium oxyallyl cations are predicted to react with 1,3‐butadiene both in a stepwise fashion and via concerted [4 + 3] cycloaddition with so‐called extended stereochemistry. With hydroxyallyl cation, the stepwise process is preferred and subsequent second bond closures generate products equivalent to those that would arise from concerted [4 + 3] or [3 + 2] cycloadditions. For lithium and sodium oxyallyl cations, concerted, asynchronous processes are predicted to be preferred over stepwise processes, with [3 + 2] cycloaddition to generate a 3 H ‐dihydrofuran followed by Claisen rearrangement of that intermediate being the lowest energy pathway for formation of a seven‐membered ring. In the case of uncharged 2‐oxyallyl, only transition state structures for concerted cycloadditions appear to exist. We infer that for [4 + 3] cycloadditions, concerted pathways are preferred over stepwise pathways provided that the separation between the electrophilicity of the allyl component and the electrofugacity of the 4π component is not too large. The Hammond postulate is shown to rationalize variations in free energies of activation for different processes as a function of allyl electrophilicity. Factors influencing the stereochemical outcome of different cycloadditions are discussed. Copyright © 2000 John Wiley & Sons, Ltd.