Stereospecific Synthesis And Acetolysis of anti-Tricyclo[4.4.1.12′5]Dodecan-11-yl And Related Derivatives

• Published in: Canadian journal of chemistry 1975-10, Vol.53 (20), p.3078-3086
• Main Authors: Wood-Farmer, J. Hay, Friedlander, B. T, Crawford, A, Thompson, L. M, Wetzer, and W
• Format: Article
• Language: English
• ISSN: 0008-4042; 1480-3291
• DOI: 10.1139/v75-437

Stereospecific conversion of tricyclo[4.4.1.1 2,5 ]dodecan-11-one and of several related unsaturated and cyclopropanated ketones into syn or anti alcohols is described. Acetolysis of anti-tricyclo[4.4.1.1 2 ' 5 ]dodecan-11-yl p-bromobenzenesulfonate, anti-tricyclo[4.4.1.1 2 ' 5 ]dodec-3-en-11-yl p-bromobenzenesulfonate, anti;-tetracyclo[5.4.1.1 2,6 .0 3,5 ]tridecan-12-yl p-bromobenzenesulfonate each proceeds at about the same rate as other equatorial cyclohexyl p-bromobenzenesulfonates to give complex mixtures of rearranged acetates and hydrocarbons. No evidence for neighboring group participation by the remote double bond or cyclopropane ring in these esters was found. The stereochemically interesting ketone reductions, the unambiguous structural proofs of the reduction products, and possible explanations of the solvolysis rates are discussed.