de Meijere, Armin; von Seebach, Malte; Zollner, Stefan; Kozhushkov, Sergei I.; Belov, Vladimir N.; Boese, Roland; Haumann, Thomas; Benet-Buchholz, Jordi; Yufit, Dmitrii S.; Howard, Judith A. K.:
Spirocyclopropanated bicyclopropylidenes: straightforward preparation, physical properties, and chemical transformations.
2001
In: Chemistry--A European Journal, Jg. 7 (2001), Heft 18, S. 4021 - 4034
Artikel/Aufsatz in Zeitschrift / Fach: Chemie
Titel:
Spirocyclopropanated bicyclopropylidenes: straightforward preparation, physical properties, and chemical transformations.
Autor(in):
de Meijere, Armin; von Seebach, Malte; Zollner, Stefan; Kozhushkov, Sergei I.; Belov, Vladimir N.; Boese, Roland im Online-Personal- und -Vorlesungsverzeichnis LSF anzeigen; Haumann, Thomas; Benet-Buchholz, Jordi; Yufit, Dmitrii S.; Howard, Judith A. K.
Erscheinungsjahr
2001
Erschienen in:
Chemistry--A European Journal, Jg. 7 (2001), Heft 18, S. 4021 - 4034
ISSN

Abstract:

The prepn., crystal structures, phys. properties, and reactions of spirocyclopropanated bicyclopropylidenes such as I were studied. I was prepd. in three steps and 24% yield from 7-cyclopropylidenedispiro[2.0.2.1]heptane, or, more efficiently, in one step by a dehalogenative coupling of 7,7-dibromo[3]triangulane II (82%). Reductive dimerization was also used successfully in the prepn. of (E)- and (Z)-bis(spiropentylidene) and even of the \"third-generation\" spirocyclopropanated bicyclopropylidene III (17% yield over three steps from II). Whereas the parent bicyclopropylidene dimerized at 180 DegC to yield [4]rotane, dimerization of I at 130 DegC under 10 kbar pressure occurred only with opening of one three-membered ring to yield the polyspirocyclopropanated (cyclopropylidene)cyclopentane deriv. IV in 34% yield; at elevated temp., the polyspirocyclopropanated 2-cyclopropylidene[3.2.2]propellane deriv. V was isolated in 25% yield. I and III underwent addn. of bromine, hydrogen bromide, and various dihalocarbenes to the central double bond without rearrangement. A branched [7]triangulane and a branched dichloro-C2v-[15]triangulane were used to prep. perspirocyclopropanated [3]rotane (D3h-[10]triangulane) VI (in six steps and in 1.4% overall yield from I) and the C2v-[15]triangulane VII (in two steps and in 41% overall yield from III). Catalytic hydrogenation of I yielded 7,7'-bis(dispiro[2.0.2.1]-heptyl) and, under more forcing conditions, 1,1'-bis(2,2,3,3-tetramethylcyclopropyl). The bromofluorocarbene adduct of III reacted with butyllithium to give an unexpected polyspirocyclopropanated cyclopropylidenebicyclohexane deriv. as the main product along with the expected \"third-generation\" perspirocyclopropanated dicyclopropylidenemethane. Mechanistic aspects of the prepn. and reactions of spirocyclopropanated bicyclopropylidenes are discussed. The structures were characterized by X-ray crystal structure anal.; structural and crystal packing features are presented.