154701-26-5Relevant academic research and scientific papers
Wagner-Meerwein Rearrangement of 4-Hydroxymethylpentacyclo2,5.03,8.04,7>nonane to Pentacyclo2,6.03,9.04,8>decane in Formic Acid
Hasegawa, Takeshi,Kuwatani, Yoshiyuki,Higuchi, Hiroyuki,Ueda, Ikuo
, p. 3009 - 3014 (1993)
The cationic rearrangement of 1-bromo-4-pentacyclononane-9-spiro-2'-dioxolane (1) in formic acid gave 4-bromo-1-formyloxy-10,10-bis(4-methoxyphenyl)pentacyclodecane-5-spiro-2'-dioxolane in 27percent yield along with 5-bromo-9-formyloxy-10,10-bis(4-methoxyphenyl)pentacyclodecane-6-spiro-2'-dioxolane in 55percent yield. The reaction of 1 with p-toluenesulfonic acid or hydrochloric acid in methanol also afforded 4-bromo-1-methoxy-10,10-bis(4-methoxyphenyl)pentacyclo decane-5-spiro-2'-dioxolane together with 5-bromo-9-methoxy-10,10-bis(4-methoxyphenyl)pentacyclodecane-6-spiro-2'-dioxolane. With respect to migration of the C4-C5 bond in the pentacyclononane (homocubane) skeleton to pentacyclodecane (D 2h -bishomocubane), a rearrangement into the bishomocubane system is driven by a concomitant release of strain; also, the stability of the 4-homocubanemethyl cation intermediate may play an important role in determining the course of the cage expansion into the D 2h -bishomocubane system. This reaction provides an attractive route for the synthesis of bishomocubane bridgehead alcohols and related compounds which are not easily accessible by other routes.
