- Epoxidation of Barrelene: Preparation and Properties of Oxahomobarrelenes
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A four-step synthesis makes barrelene (1) readily accessible on a 1-2 g scale.Upon epoxidation with KHCO3-buffered m-chloroperbenzoic acid 1 yields the mono- (2b), both the endo,exo- and exo,exo-isomeric bis- (3b and 4b) as well as the trisepoxide 5b.In the presence of traces of acid 2b very rapidly rearranges to cycloheptatriene-7-carbaldehyde (15), 5b undergoes a facile acid-catalyzed rearrangement to 4,7,11-trioxatrishomocubane (16).Under basic and neutral conditions 5b is stable towards virtually any nucleophile, its three epoxide rings can only be opened underreductive conditions with solvated electrons.On the other hand, endo,exo-dioxadihydrobishomobarrelene 20 and oxatrishomobarrelene 23 are readily attacked at the oxirane rings by lithium iodide/disodium hydrogen phosphate.
- Weitemeyer, Christian,Preuss, Thomas,Meijere, Armin de
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p. 3993 - 4005
(2007/10/02)
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- SYNTHESIS OF TETRACYCLO2,4.03,6>OCT-7-ENE AND SOME OF ITS DERIVATIVES
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A full account is given of the synthesis of the title compound, its 7,8-dihydro-analogue and of some of its derivatives.
- Stapersma, J.,Rood, I. D. C.,Klumpp, G. W.
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p. 191 - 199
(2007/10/02)
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