Theoretical study of the regioselectivity of the cycloaddition reaction between cyclopentadiene and methyleneketene

Three possible reaction schemes for the cycloaddition reaction between methyleneketene and cyclopentadiene were studied by DFT (density functional theory) and ab initio calculations. All of these cycloaddition reactions are exothermic, concerted but nonsynchronous processes. The computed activation energies indicate that the norbornene product yielded from a 1,2-addition of methyleneketene with cyclopentadiene (reaction (1)) is the primary product. The performance of various computational methodologies, MP2, MP4, and CCSD(T), in conjunction with a wide array of basis sets, 6-31G(d), 6-311+G(d,p), aug-cc-pVDZ, and aug-cc-pVTZ, in obtaining reliable activation and reaction energies of the reactions under investigation has been critically analyzed. (c) 2006 Elsevier Ltd. All rights reserved.