Tricyclo[4.2.2.22,5] dodecane and Tricyclo [4.2.2.12,5]undecane. Preliminary communication

A synthesis of tricyclo [4.2.2.2^2,5]dodecane ( 19 ), a novel tricyclic C₁₂H₂₀ compound, is described. The key intermediate ketone 13 was prepared either from the C₁₀-photodimer 1 of cyclopentadienone or the C₁₁-cycloaddition products 11 and 12 . 13 was also transformed to tricyclo [4.2.2.1^2,5]undecane ( 8 ).     

Synthesis of Tricyclo[4.4.0.02,7]decane Derivatives from Tricyclo[4.1.0.02,7]heptane Precursors

Russian Journal of Organic Chemistry - Tricyclo[4.1.0.02,7]heptane and 1-phenyltricyclo[4.1.0.02,7]heptane reacted with 2,3-bis(benzenesulfonyl)propene in boiling toluene (20–24 h) in the...     

The Adamantane Rearrangement of Tricyclo[4.2.2.01,5]decane to Tricyclo[5.3.0.04,8]decane

Regioselective generation of the C(2)-carbocation a of tricyclo[4.2.2.0^1,5]decane ( 1 ) by treatment of both corresponding epimeric alcohols 5 and 6 with BF₃ and trapping the rearranged tricyclo[5.3.0.0^4,8]decan-7-yl carbocation b with Et₃SiH as hydride-ion donor (ionic hydrogenation) gives the corresponding hydrocarbon 3 as sole product in almost quantitative yield. The latter is a known intermediate in the Lewis-acid-catalyzed rearrangement of 1 to adamantane ( 4 ).     

Tricyclo[2.1.0.01,3]pentane

The reaction of 1,1-dibromo-2,3-bis(chloromethyl)cyclopropane with methyllithium leads initially to ring closure to 1-bromo-2-chloromethylbicyclo[1.1.0]butane. Further reaction leads to an unstable compound which reacts with phenylthiol to give 2-vinyl-1-cyclopropyl phenyl sulfide and undergoes thermal rearrangement at ∼ -50°C to give cyclopentadiene. Strong evidence is presented which suggests that tricyclo[2.1.0.01,3]pentane may be the intermediate.     

Photochemical Selenosulfonation of Tricyclo[4.1.0.02,7]heptane Derivatives

Russian Journal of Organic Chemistry - Se-Phenyl methane-, benzene-, and 4-methylbenzenesulfonoselenoates PhSeSO2R (R = Me, Ph, 4-MeC6H4) react with 1-X-tricyclo[4.1.0.02,7]heptanes (X = Me, Ph,...     

Iodination of Tricyclo[4.1.0.02,7]heptane in the Presence of External Nucleophiles

Tricyclo[4.1.0.02,7]heptane reacted with iodine, N-iodosuccinimide, and iodine monochloride in the presence of external nucleophiles yielding products of conjugate endo,syn addition at the central C¹-C⁷ bond. The mechanism of these chemo- and stereoselective reactions is discussed.     

Carbon Atom Insertion: A One-Step Synthesis of Tricyclo[3.2.1.02,7]octanes and Tricyclo[4.1.0.02,7]heptanes from Cyclohexenes1

Reinarz and Fonken have reported² that the dibromocarbene adduct (1) of 1-methylcyclohexene, upon reaction with methylllthium at 0° in ether, produced exclusively the bicyclobutanes 2 and 3 in relative yields of 60% and 40%, respectively. We have prepared 1 by the phase-transfer method³ of Makosza and Fedorynski in a yield of 67%, found these previous results to be completely reproducible in our hands, and determined the combined yield of the two products (2 and 3) to be 67% also. Thus, the overall