Chemistry of strained polycyclic compounds—III: Synthesis of cubane and homocubane alcohols

Abstract The synthesis of three bridgehead alcohols, viz. 1-bromo-4-hydroxypentacyclo[4.3.0.0 2,5 .0 3,8 .0 4,7 ]nonan-9-one ethylene ketal ( 8 ), 1-bromo-4-hydroxypentacyclo[4.3.0.0 2,5 .0 3,8 .0 4,7 ]nonane ( 18 ) and 1-bromo-4-hydroxypentacyclo[4.2.0.0 2,5 .0 3,8 .0 4,7 ]octane ( 24 ) is described. Two routes were considered: solvolysis of the corresponding acetates and deamination of the bridgehead amines. The deamination of homocubane 4-amines 11 and 15 , and of cubane amine 23 has been studied under various conditions. An improved cage-contraction of homocubane derivatives to substituted cubanes is described. Despite the increase in ring strain cubane alcohol 24 appeared to be more stable than homocubane alcohols 8 and 18 .

[1]  J. R. Hoover,et al.  Synthetic studies related to the bird-cage system. III. Derivatives of pentacyclo[5.4.0.02,6.03,10.05,9]undecane, tetracyclo[4.4.0.0.3,9.04,8]decane, and pentacyclo[4.4.0.02,5.03,9.04,8]decane , 1970 .

[2]  T. Fukunaga.  Isomerization via Transannular Enolate Anion , 1965 .

[3]  C. Ganter,et al.  Nuclear Magnetic Resonance Spectroscopy. Ring Inversion in 3,5,7-Cyclooctatrienone , 1966 .

[4]  H. Prinzbach,et al.  Basenkatalysierte Umlagerungen im Tetracyclo[3.3.0.02.8.04.6]octan‐System , 1969 .

[5]  A. Padwa,et al.  Photochemical transformations of small ring carbonyl compounds. XXXIX. Photochemical synthesis and chemical reactivity of the tricyclo(3.2.0.0 2,6 )heptan-7-ol system. , 1972, Journal of the American Chemical Society.

[6]  M. Rathke,et al.  Reaction of lithium N-isopropylcyclohexylamide with esters. Method for the formation and alkylation of ester enolates , 1971 .

[7]  B. Zwanenburg,et al.  Chemistry of strained polycyclic compounds—VI : Stereospecific base induced homoketonization of cubane, homocubane and 1,3-bishomocubane bridgehead alcohols , 1973 .

[8]  C. Bugg,et al.  An x-ray diffraction study of nonplanar carbanion structures. , 1964 .

[9]  B. Zwanenburg,et al.  Chemistry of strained polycyclic compounds—V : The stereospecific cationic cage expansion reaction of 4-homocubane carbinols to 1,3-bishomocubane bridgehead alcohols , 1973 .

[10]  S. J. Cristol,et al.  Communications. A Convenient Synthesis of Alkyl Halides from Carboxylic Acids , 1961 .

[11]  R. Howe,et al.  Homoenolization-Homoketonization of a Half-Cage Ketone1,2 , 1965 .

[12]  A. Nickon,et al.  Bridged Ring Systems by Anionic Rearrangement1 , 1965 .

[13]  D. Covey,et al.  ACID HOMOKETONIZATION WITH INVERSION OF CONFIGURATION, A DRAMATIC EFFECT OF WATER IN CONTROL OF STEREOCHEMISTRY , 1974 .

[14]  K. Toyne,et al.  Preparations and properties of caged polycyclic systems. 1. Pentacyclo[5.3.0.02,5.03,9.04,8]decane and pentacyclo[4.3.0.02,5.03,8.04,7]nonane derivatives , 1970 .

[15]  N. H. Werstiuk,et al.  Homoenolization and Related Phenomena. VI.1 Stereospecificity in Alkaline and Acid Media2,3 , 1966 .

[16]  F. Anet,et al.  The Effects of Steric Compression on Chemical Shifts in Half-Cage and Related Molecules1,2 , 1965 .

[17]  C. Nenitzescu,et al.  Untersuchungen in der Cyclobutanreihe, XII. Zwei stereoisomere Dimere des Cyclobutadiens , 1964 .

[18]  D. Cram,et al.  Electrophilic substitution at saturated carbon. XLI. Equilibrium constants, absolute configurations, and maximum rotations of cis- and trans-1,2-dimethyl-2-phenylcyclopentanols and their base-catalyzed cleavage products , 1969 .

[19]  K. Scherer,et al.  Formation of a Bridgehead Radical by Diazotization of an Aliphatic Amine1 , 1966 .

[20]  T. W. Cole,et al.  The Cubane System , 1964 .

[21]  D. Cram,et al.  Electrophilic substitution at saturated carbon. XLII. Trimethylene keto carbanions as intermediates in base-catalyzed epimerization, racemization, and cleavage reactions of optically active diastereomers of 1,2-dimethyl-2-phenylcyclopentanols , 1969 .

[22]  W. Dilling,et al.  Pentacyclodecane chemistry—II: Some reactions of dodecachloropentacyclo[5.3.0.0.2,6.03,9.04,8]decane and related compounds , 1967 .

[23]  J. Weinstock.  Notes- A Modified Curtious Reaction , 1961 .

[24]  W. Dilling,et al.  Pentacyclodecane chemistry—III: Fragmentation patterns of pentacyclodecane derivatives on electron impact , 1967 .