de Meijere, Armin; Von Seebach, Malte; Kozhushkov, Sergei I.; Boese, Roland; Blaser, Dieter; Cicchi, Stefano; Dimoulas, Tula; Brandi, Alberto:

Cyclopropyl building blocks for organic synthesis, 72. Cyclobutylidenecyclopropane: new synthesis and use in 1,3-dipolar cycloadditions - a direct route to spirocyclopropane-annulated azepinone derivatives.

In: European Journal of Organic Chemistry, (2001) ; Nr. 20, S. 3789-3795
ISSN: 1434-193X
Zeitschriftenaufsatz / Fach: Chemie
(cyclopropylidene)cyclobutane was prepd. in multi-gram quantities by a new three-step sequence starting from Et cyclobutanecarboxylate. The 1,3-dipolar cycloaddn. of N-(phenylmethylene)methanamine, N-(2-pyridinylmethylene)methanamine and 1,4-dioxa-7-azaspiro[4.4]non-6-ene 7-oxide onto (cyclopropylidene)cyclobutane resulted in the regioselective formation of the corresponding adducts [i.e., dispiro[(cyclobutane)isoxazolidine(cyclopropane)] derivs.], with the spirobutane moieties adjacent to the oxygen atom in the oxazolidine rings. Under flash vacuum pyrolysis conditions, these cycloadducts furthermore underwent thermal rearrangement with opening of the four-membered ring, to afford spiro[cyclopropane]azepinones. In one case, an indolizidinone was also isolated (13% yield). Mechanistically this rearrangement is interpreted in terms of a cyclobutylmethyl-to-penten-5-yl radical rearrangement.