Regio- and stereospecific ring-opening reactions of 4-substituted basketanes and seco-basketanes

Synthesis and chemistry of homocubanes, bishomocubanes, and trishomocubanes

“…These reactions are summarized in Scheme 24. 53 Cationic skeletal rearrangements have been observed in the basketane system. Thus, treatment of pentacy- Solvolytic reactions of appropriately substituted basketanes have been studied.…”

“…These reactions are summarized in Scheme 24. 53 Cationic skeletal rearrangements have been observed in the basketane system. Thus, treatment of pentacy- 1.…”

Strained bridgehead cage alcohols and derivatives

“…The half-cage ketones 100 derived from the corresponding basketane bridgehead acetates 7 could only be isolated by using short reaction times. 72 Prolonged base treatment induced further breakdown to the bicyclooctene esters 101. It is noteworthy that such an extended degradation was not observed in the case of secohomocubanones 98.…”

“…The reactivity of the cubane-type alcohols (or acetates) in this homoketonization process grosso modo parallels the total cage strain energy: cubane > basketane ~homocubane > 1,3-bishomocubane.4'5'15 '71,72 The basketane system is anomalous since basketyl acetate homoketonizes much faster than the more strained homocubyl acetate. 72 This increased reactivity is probably attributable to the outbending effect of the ethylene bridge, which increases the strain around the C4 and C5 atoms in basketane relative to homocubane. The structural features of homocubane and basketane derivatives, determined by X-ray diffraction analyses,73 show clearly that the C-C bonds around C4 and C5 in basketane are in fact somewhat compressed compared with those in the homocubane system.…”