期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 16, 期 40, 页码 12147-12157出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201001714
关键词
aromaticity; catalysis; cycloadditions; density functional calculations; reaction mechanisms
资金
- Spanish MICINN [CTQ2007-67528, CSD2007-00006, S2009/PPQ-1634]
- Spanish CAM [CTQ2007-67528, CSD2007-00006, S2009/PPQ-1634]
- Gobierno Vasco-Eusko Jaurlaritza [IT-324-07]
- Xunta de Galicia [INCITE09209122PR]
The thermal [4+3] cycloaddition reaction between allenes and tethered dienes (1,3-butadiene and furan) assisted by transition metals (Au-I, Au-III, Pd-II, and Pt-II) was studied computationally within the density functional theory framework and compared to the analogous non-organometallic process in terms of activation barriers, synchronicity and aromaticity of the corresponding transition states. It was found that the metal-mediated cycloaddition reaction is concerted and takes place via transition structures that can be even more synchronous and more aromatic than their non-organometallic analogues. However, the processes exhibit slightly to moderately higher activation barriers than the parent cycloaddition involving the hydroxyallylic cation. The bond polarization induced by the metal moiety is clearly related to the interaction of the transition metal with the allylic pi* molecular orbital, which constitutes the LUMO of the initial reactant. Finally, replacement of the 1,3-butadiene by furan caused the transformation to occur stepwise in both the non-organometallic and metal-assisted processes.
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