title: 4-Oxatricyclo[5.2.1.0(2,6)]decan-10-one and 4-oxatricyclo[5.2.1.0(2,6)]dec-8-en-10-one. Experimental and DFT investigations of the pi-selectivities.
abstract: Ab initio MO and experimental pi-selectivities of hydride additions to 4-oxatricyclo[5.2.1.0(2,6)]decan-10-one and 4-oxatricyclo[5.2.1.0(2,6)]dec-8-en-10-one are described. The interactions of sigma(C1-C2) and sigma(C6-C7) with pi(C=O), on one hand, and those of sigma(C1-C9) and sigma(C7-C8) with pi(C=O), on the other hand, support anti-selectivities for both. This is in full accordance with the experiments. The arguments that are based on electrostatic interactions and electron donation from the ring oxygen do not apply.
authors.affiliation: Department of Chemistry, Indian Institute of Technology, Kanpur 208 016, India. vijendra@iitk.ac.in
authors.forename: Veejendra K
authors.initials: VK
authors.lastname: Yadav
authors.forename: Rengarajan
authors.initials: R
authors.lastname: Balamurugan