4- tricyclo decane

The synthesis of adamantane (15), tricyclo[3.3.1.1 ]decane [281-23-2] by heating tetrahydrodicyclopentadiene (14) [6004-38-2] in the presence of aluminum trichloride illustrates another aspect of the synthetic utiHty of DCPD (80). Adamantane is the base for dmgs that control German measles and influenza (80-81) (see ANTIVIRAL AGENTS). 

CPD is the starting material for 8-hydroxymethyl-tricyclo[5.2.1.0 ] decane [57286-50-8] (16) (or octahydro-4,7-methano-lJT-indene-5—methanol), which is in turn converted into 3-halo-4-homoisotwistane (17), an intermediate for antiviral dmgs (82). 

The conversion of tricyclo-[4,4,0,0]-decan-4-one (237) into the moiiodeutera-ted hydrindanone (238) serves as a good illustration of this labeling proce-... 

Adamantane (CAS No 281-23-2) l-tricyclo[3.3.1.1 ]decane is a cage hydrocarbon with a white or almost white crystalline solid nature, like solid wax, at normal conditions. Its odor resembles that of camphor. It is a stable and nonbiodegradable compound that is combustible due to its hydrocarbon nature. It has not been found to be hazardous or toxic to living entities [14, 15]. It should be pointed out that adamantane can exist in gas, liquid, and two solid crystalline states. 

Tri-o-cresyl phosphate, t452 Tricyclene, t400a Tricyclo[3.3.1.13=7]decane, a65... 

Tricyclo[5.2.1,02-6]decane-4,8-dimethanol, b202 3-Triethoxysilylpropylamine, a273 Triethyl borate, t268... 

Figure 5. Ar,Ar,Ar-Trimethyl-8-tricyclo[5.2.1.02 S]decane ammonium cation (3) template for SSZ-33.

The skeleton of 47 is a heterocyclic tricyclo[6.2.0.0 ]decane and the similarity to the tricyclic kelsoene is obvious. In the course of the above-mentioned studies we had become curious whether the high facial diastereocontrol in the photocycloaddition reaction could be extended to other bridged 1,6-hexadienes. Kelsoene was an ideal test case. The retrosynthetic strategy for kelsoene along an intramolecular [2+2]-photocycloaddition pathway appeared straightforward. To avoid chemoselectivity problems the precursor to kelsoene should not contain additional double bonds. Alcohol 48, the hydroxy group of which was possibly to be protected, seemed to be a suitable substrate for the photocycloaddition (Scheme 14). Access to the 1,2,3-substi-... 

Neben trans-Tricyclo [5.3.0.0 decan (30) als Hauptprodukt werden nocb eine Anzabl anderer Koblenwasserstoffe (31—34) bei der Bestrah-lung von Cyclopenten in Aceton-Losung mit Licbt der Wellenlange A > 270 m[ji gebildet (26) ... 

Wiseman and coworkers have succeeded in preparing tricyclo[5.3.0.0 ]decane (393), a CioHig hydrocarbon which unlike adamantane is chiral. Their elegantly simple approach entails Diels-Alder addition of cyclobutene to l,4-dihalocyclohexa-l,3-dienes, catalytic hydrogenation of the adduct, reaction with aluminium triiodide, and ultimately di- -butyltin dihydride reduction. 

The isomeric tricyclo[3.3.2.0 ]decane hydrocarbon (396) has also recently yielded to synthesis Thus, reaction of 394a with either thionyl chloride or phosphorus pentachloride led to rearrangement and formation of chloride 395a. Alternatively,... 

Ganter has developed three different approaches to tricyclo[5.2.1.0 ]decane (403), yet another of the nineteen isomeric hydrocarbons of adamantaneland As seen in Scheme XXXIII, the routes involve intramolecular cyclization of keto tosylate 399 followed by Wolff-Kishner reduction of the resulting ketone, thermo-cyclization of 400 and subsequent dechlorination, hydrogenation, and photocycli-zation of aldehydes 401. Majerski s approach involved hypoiodite cleavage of alcohol 402... 

Two very similar and very direct approaches serve to make tricyclo[5.2.1.0 ]-decane (408) readily available... 

The comparison of the genuine theoretical results with those predicted by this approximation shows a root-mean-square (rms) deviation of 0.2kcal/mol with those obtained in the HF/6-31G(if) calculations reported in Table 9.1. This result is all the more remarkable as it includes polycychc molecules (15-21), boat-cyclohexane stmctures (15, 21), as well as a twist-boat structure (19, twistane = tricyclo [4.4.00 ]decane). The use of this approximation for ZPE + — Hq in problems... 

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