4-Oxatricyclo[5.2.1.0 < sup > 2,6 < /sup > ]decan-10-one and 4-oxatricyclo[5.2.1.0 < sup > 2,6 < /sup > ]dec-8-en-10-one. Experimental and DFT investigations of the π-selectivities

Abstract

Ab initio MO and experimental π-selectivities of hydride additions to 4-oxatricyclo [5.2.1.02,6]decan-10-one and 4-oxatricyclo[5.2.1.02,6]dec-8-en-10-one are described. The interactions of σC1-C2 and σC6-C7 with π*C=O, on one hand, and those of σC1-C9 and σC7-C8 with π*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.