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Roofed polyquinanes: synthesis and electronic structure

Mehta, Goverdhan and Reddy, Raja K and Gleiter, Rolf and Lalitha, S and Chandrasekhar, Jayaraman (1991) Roofed polyquinanes: synthesis and electronic structure. In: Journal of Organic Chemistry, 56 (25). 7048 -7055.

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Official URL: http://pubs.acs.org/doi/abs/10.1021/jo00025a019

Abstract

Starting from readily available norbornenobenzoquinone 7 and employing a photothermal metathesis reaction as the main strategy, novel "roofed" polyquinane bisenones 3 and 13 have been synthesized. Among these, the former is potentially serviceable for further elaboration to dodecahedrane 1. Catalytic hydrogenation of 3 provided the dione 12, which fully inscribes the circumference of dodecahedrane sphere. The "roofed" C-16-bisenone 3 has been successfully annulated to C19-bisenone 24 and C19-trisenone 26 by employing the Greene methodology and Pauson-Khand reaction, respectively. The molecular structures of 3 and 13 were computed using molecular mechanics and semiempirical MO methods. The nonbonded distances between the double bonds vary strongly with the method employed. The interactions between the pi-MO's were, therefore, probed by means of photoelectron (PE) spectroscopy. Comparison with the PE spectra of a series of model systems with increasing complexity enabled an unambiguous assignment of the observed peaks. The symmetric and antisymmetric combinations of the pi-MO's of the enone moieties of 3 and 13 show large splittings, characteristic of propano-bridged systems in which through-space and through-bond effects act in concert.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to American Chemical Society.
Keywords: Through-Space Interactions;Ground-States;Dodecahedrane; Molecules;Design;CyclopentanoneDerivatives;Reactivity; Olefins;Route.
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Date Deposited: 30 Nov 2010 06:24
Last Modified: 30 Nov 2010 06:24
URI: http://eprints.iisc.ernet.in/id/eprint/34121

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