Palladium-mediated fragmentation reactions of meta photocycloadducts to afford arylated or oxidatively cyclised products

Whilst seeking to improve the yield of a Heck-style arylation/fragmentation reaction using a silyloxy substituted meta photocycloadduct, an alternative reaction pathway was discovered that led to the formation of the unique oxidatively cyclised compound 8. This tricyclic ether is believed to form as...

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Published inTetrahedron Vol. 62; no. 40; pp. 9403 - 9409
Main Authors Penkett, Clive S., Sims, Rupert O., Byrne, Paul W., Berritt, Simon, Pennicott, Lewis E., Rushton, Stephen P., Avent, Anthony G., Hitchcock, Peter B.
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier Ltd 02.10.2006
Elsevier
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
ALCOHOLS
STONE
INTRAMOLECULAR HECK REACTION
CATALYZED ALLYLIC ALKYLATIONS
CYCLIZATION
MOLECULAR-OXYGEN
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Summary:Whilst seeking to improve the yield of a Heck-style arylation/fragmentation reaction using a silyloxy substituted meta photocycloadduct, an alternative reaction pathway was discovered that led to the formation of the unique oxidatively cyclised compound 8. This tricyclic ether is believed to form as the result of the meta photocycloadduct structure fragmenting to give a π-allyl palladium species and then subsequently being displaced by a neighbouring hydroxyl group. An attempt to develop an enantioselective version of this reaction via the desymmetrisation of a meso π-allyl palladium intermediate was made using the meta photocycloadduct derived from anisole and Z-but-2-ene-1,4-diol, however no enantioenrichment of the products could be detected. [Display omitted]
Bibliography:researchfish
ISSN:0040-4020
1464-5416
DOI:10.1016/j.tet.2006.07.060