期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 73, 期 6, 页码 2083-2089出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo702257s
关键词
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The thermal Diels-Alder reaction between alkenylmetal(0) Fischer carbenes and 1,3-dienes (isoprene and cyclopentadiene) has been Studied computationally within the density functional theory framework. The selectivity of the [4 + 2] cycloadditions between alkenyl-group 6 (Fischer) carbene complexes and isoprene is similar to the selectivity computed for the reactions involving Lewis acid complexed acrylates. The experimentally observed complete endo selectivity in the [4 + 2] cycloadditions of alkenyl-group 6 (Fischer) carbene complexes with cyclopentadiene, which takes place under kinetic control, may be due in part to the presence of stabilizing secondary orbital interactions. These interactions are stronger than the analogues in the metal-free processes. The [4 + 2] cycloadditions between alkenyl-group 6 (Fischer) carbene complexes and neutral dienes occur concertedly via transition structures which are more asynchronous and less aromatic than their non-organometallic analogues, a behavior which is extensible to the reactions between Lewis acid complexed acrylates.
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