Synthesis of the Cyclobutanone Core of Solanoeclepin A via Intramolecular Allene Butenolide Photocycloaddition.

Abstract

Synthesis of the Cyclobutanone Core of Solanoeclepin A via Intramolecular Allene Butenolide Photocycloaddition. -Title compound (I) is a potent hatching agent of potato cyst nematodes. -(HUE, B. T. B.; DIJKINK, J.; KUIPER, S.; LARSON, K. K.; GUZIEC, F. S. J.; GOUBITZ, K.; FRAANJE, J.; SCHENK, H.; VAN MAARSEVEEN, J. H.; HIEMSTRA*, H.; Org. Biomol. Chem. 1 (2003) 24, 4364-4366; Inst. Mol. Chem., Univ. Amsterdam, NL-1018 WS Amsterdam, Neth.; Eng.) -Nuesgen 20-029

Recent Advances in the Synthesis of Cyclobutanes by Olefin [2 + 2] Photocycloaddition Reactions

“…561−566 A representative model reaction rac-307 → rac-308 is depicted in Scheme 99. 561 In an approach to conformationally rigid pyrrolidines and bis-pyrrolidines the intramolecular [2 + 2] photocycloaddition of various 4-(allylaminomethyl)-2(5H)-furanones was investigated. 567−569 The reactions (e.g.…”

“…If the tether between the reacting olefin and the enone double bond of a 5-substituted 2­(5 H )-furanone is too short to allow for a straight [2 + 2] photocycloaddition, the crossed addition mode prevails. Hiemstra and co-workers studied this reaction class intensively in possible approaches toward the synthesis of (±)-solanoeclepin A. − A representative model reaction rac - 307 → rac - 308 is depicted in Scheme …”

Recent Synthetic Applications of Catalyst-Free Photochemistry

“…Besides the intermolecular cycloaddition involving allene, Hiemstra et al employed an intramolecular allene/enone [2+2] cycloaddition to prepare the cyclobutanone core of solanoeclepin A. 17 Wege and Nielsen also achieved the total synthesis of elecanacin through an intramolecular naphthoquinone-vinyl ether photochemical cycloaddition. 18 Scheme 2 Enone and olefin cycloaddition in the total synthesis of allocyathin B 3 Similarly, Figueredo, Font and co-workers developed an enantioselective synthesis of (+)-grandisol, which contains a cyclobutane motif (Scheme 3).…”

Thermally-induced intramolecular [2 + 2] cycloaddition of allene-methylenecyclopropanes: expedient access to two separable spiropolycyclic heterocycles

“…6 In the meantime, Hiemstra's group achieved a photo-induced intramolecular [2 + 2] cycloaddition reaction in allene and butenolide containing substrates upon UV light irradiation for the rapid construction of a key cyclobutanone core of solanoeclepin A [Scheme 1B (b)]. 7 Moreover, the thermally-induced intramolecular [2 + 2] cycloaddition reaction is an extremely useful and common strategy for the construction of a cyclobutane structural motif as well. For instance, Tanaka's group first discovered that unactivated ene-allenic and yne-allenic substrates can regioselectively undergo intramolecular [2 + 2] cycloaddition between the distal double bond of the allene moiety and the olefinic unit, giving bicyclic heterocycles in a fully diastereoselective manner upon heating without any additive (Scheme 1C).…”