Studies towards the total synthesis of solanoeclepin A: synthesis of the 7-oxabicyclo[2.2.1]heptane moiety and attempted seven-membered ring formation

Autor:	Angeline E. van Ginkel, Jorg C. J. Benningshof, Jan H. van Maarseveen, Floris P. J. T. Rutjes, Richard H. Blaauw, Henk Hiemstra
Rok vydání:	2002
Předmět:	chemistry.chemical_classification chemistry.chemical_compound Chiral auxiliary Enantiopure drug chemistry Stereochemistry Diol Moiety Total synthesis Ring (chemistry) Aldehyde Lactone
Zdroj:	Journal of the Chemical Society, Perkin Transactions 1. :1693-1700
ISSN:	1364-5463 1472-7781
DOI:	10.1039/b201987f
Popis:	This paper details studies towards the total synthesis of solanoeclepin A (1), the most active natural hatching agent of potato cyst nematodes. The first goal was the preparation of the tetracyclic left-handed substructure 2 in enantiopure form. The 7-oxabicyclo[2.2.1]heptane moiety was obtained via a diastereoselective intramolecular Diels–Alder strategy by using (R)-phenylglycinol as a chiral auxiliary as pioneered by Mukaiyama. A chromium-mediated nickel-catalysed coupling of aldehyde 5 with vinyl triflate 6 gave α,β-unsaturated lactone 18 as a single stereoisomer. The seven-membered ring was expected to arise from a McMurry coupling of dialdehyde 4. Surprisingly, oxidation of diol 24 did not lead to the desired dialdehyde 4, but to the eight-membered ring lactone 25.
Databáze:	OpenAIRE
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