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Theoretical investigation of intramolecular singlet carbene 1,4- and 1,2-cycloadditions

Evanseck, Jeffrey D.
Houk, Kendall N.
Published in Journal of the American Chemical Society. 1990, vol. 112, no. 1, p. 73-80
Abstract The intramolecular cycloaddition of singlet 2,4-~yclopentadienyIcarbenteo form benzvalene and reactions of related systems have been studied with ab initio molecular orbital theory. These systems were methylene plus butadiene and the intramolecular reactions of allylmethylene, 2cyclopropenykcarbene, 2-cyclobutenylcarbe.ne, and 2-cyclopentenylcarbene. Geometry optimizations were performed with restricted Hartree-Fcck calculations and the 3-21G.basis set. The effect of electron correlation was included with second-order Mdler-Plesset theory with the 6-31G* basis set on the 3-21G optimized geometries. The energies of activation were found to be dependent upon ring strain and spatial orientation of the filled carbene in-plane hybrid orbital during the initial electrophilic phase of the carbene addition. A decrease in activation energy for intramolecular cycloadditions is noted for systems that approach the idealized geometry found with intermolecular additions of carbenes to alkenes.
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EVANSECK, Jeffrey D., MAREDA, Jiri, HOUK, Kendall N. Theoretical investigation of intramolecular singlet carbene 1,4- and 1,2-cycloadditions. In: Journal of the American Chemical Society, 1990, vol. 112, n° 1, p. 73-80. https://archive-ouverte.unige.ch/unige:7901

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Deposited on : 2010-06-21

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