Photochemical preparation of tricyclic hydroxyketones by transanular cyclization of bridged 4-benzoylcyclohexanones View Full Text


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Article Info

DATE

1997-08

AUTHORS

P. Wessig, J. Schwarz, D. Wulff-Molder, G. Reck

ABSTRACT

The bridged 4-benzoyl-cyclohexanones3a–f were synthesized by α,α′-annelation of cyclic ketones. Irradiation of3a–f revealed a strong dependence of the photochemical behaviour on the ring size and the introduction of a nitrogen atom. Ketones which are able to form 1,6-biradicals (3b,c,e) undergo unselective photolytic decomposition, whereas3a,d,f afforded tricyclic hydroxyketones. The diastereoselectivity of ring closure is remarkably improved by introduction of a protected nitrogen atom (3d,f) in comparison to the carbocyclic diketone3a. Moreover, the N protective group of 4-azatricyclo-4.3.1.03,8]decan-7-one (7) could be removed affording the free hydroxy amino ketone8 in good yields. An explanation of the diastereoselective cyclization of3a and of the surprisingly low quantum yield of3d was found by conformational analysis of the corresponding triplet biradicals. More... »

PAGES

849-862

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/bf00807095

DOI

http://dx.doi.org/10.1007/bf00807095

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1037889810


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