Synthesis, Structure, and Nucleophile-Induced Rearrangements of Spiroketones

Przemyslaw Maslak; Sridhar Varadarajan; Jeffrey D. Burkey

doi:10.1021/jo990867j

Synthesis, Structure, and Nucleophile-Induced Rearrangements of Spiroketones

J Org Chem. 1999 Oct 29;64(22):8201-8209. doi: 10.1021/jo990867j.

Authors

Przemyslaw Maslak¹, Sridhar Varadarajan, Jeffrey D. Burkey

Affiliation

¹ Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802.

PMID: 11674737
DOI: 10.1021/jo990867j

Abstract

Three tetraketones based on the 2,2'-spirobiindan-1,1',3,3'-tetraone skeleton were prepared and investigated. All three compounds show spiroconjugation between their perpendicular pi-networks. The interaction results in lowering of the energy of the LUMO of the systems by ca. 0.2-0.3 eV as compared to non-spiroconjugated models. The spiroketones are susceptible to nucleophile-induced retro-Claisen condensations that lead to molecular rearrangements destroying spiro connectivity.