Quadricyclane synthesis

The incorporation of sulphonyl groups does not inhibit the cyclization process as demonstrated by Gleiter and Ohlbach133, who have reported the efficient synthesis of the quadricyclane 252 by irradiation of the norbornadiene derivatives 253. A study has also been made of the sulphonyl-substituted norbornadiene derivatives 254134 135. 

The methodology based on the reaction of 1,3-dithietanes with quadricyclane 67 was applied to the synthesis of polyfluorinated sulfur-containing polycyclic hydrocarbons. The reactions of 2,2,4,4-tetrakis(trifuoromethyl)-l,3-dithietane 66 with quadricyclane 67 under various conditions gave the cycloadduct 68 in high yields (Equation 9) <2005JFC(126)1332>. 

The synthesis of the diene (107) from the quadricyclane cycloadduct (106) reflects the value of the method (Scheme 36). 

Related to these results is the report of the first synthesis of a quadricyclane derivative 5 which is stable in water. ... 

These conversions can be applied to organic synthesis in various manners. Thus, quadricyclane can be ring opened and carbonylated with iron carbonyls.Decomplexation of the resulting acyl complex leads to a tetracyclic diketone. 

Both the acid induced and the photochemical rearrangement of the norbornaidiene derivative (146) affords the hydroxynaphthalene (147). The photo-process is not affected by triethylamine and it is thought to involve benzy lie-ally lie C-O bond cleavage. No evidence was put forward for the intermediacy of a quadricyclane. Prinzbach smd his coworkers have reported the synthesis of the oxanorbornadienes (148) and their photoconversion into the corresponding oxaquadricyclane derivatives (149) on irradiation. The azaquadricyclanes (150) have been prepared by the irradiation of the corresponding norbornadiene derivatives (151). ... 

Petrov, V.A. Davidson, E Smart, B.E. Quadricyclane— thermal cycloaddition to polyfluorinated carbonyl compounds. J. Fluorine Chem. 2004, 725(10), 1543-1552. Petrov, V.A. Stereoselective synthesis of polyfluorinated cxo-tricyclononenes and nor-bomenes. ACS Symp. Ser. 2007, 949 (Current Fluoroorganic Chemistry), 113-140. Gambaryan, N.P. Simonyan, L.A. Petrovskii, P.V. Reaction of fluoro ketones with vinyl esters. Izv. Akad. Nauk SSSR, Ser. Khim. 1967, (4), 918-921. 

Tricyclanes and Quadricyclanes.—A new synthesis of a-santalol (466) has been described. Reaction of the (7r-allyl)nickel bromide complex (464) with the bromotri-cyclene (465) gave the benzyl ether (467) and its -isomer. Reductive cleavage with... 

An improved synthesis of norbornadienone dimethyl acetal is reported which makes use of the norbornadiene-quadricyclane reversible cycloaddition. 

In contrast to bis-SiMey-norbornene derivatives, disubstituted tricyclononenes turned out to be active monomers in AP [238, 240]. In tricyclononene molecule both MesSi-groups are moved by an additional one C-C bond away from the double bond and therefore from the reaction catalytic center. Synthesis of bis-MesSi-substituted tricyclononene was carried out from quadricyclane and fran5-l,2-bis(trichlorosilyl)ethylene. This route of synthesis provided formation of norbomene-type monomers with 100% exo-configuration of cyclobutane fragment that reduced steric hindrances in AP. That is why this monomer was active in AP catalyzed with common Ni- and Pd-catalyst systems. As a result, the formation of highly molecular weight polymer (Af up to 500,000 was observed [196]. 

The Co2(CO)8-catalysed tandem 2- -2- -1/2- -2-f 2-cycloaddition reaction of terminal diynes (180) provides a simple one-pot synthesis of novel tetracyclic compounds (181) (Scheme 69). A computational study of the thermal nl + ct2 -I- a 2-cycloaddition of quadricyclane with acetylene, ethylene, DCE, and DMAD... 

Onishi, M., Hiraki, K., Itoh, H., Eguchi, H., and Abe, S., Synthesis of new ferrocenylphosphinecop-per(I) complexes and their application to the valence isomerization of norbomadiene to quadricyclane, Inorg. Chim. Acta, 145,105-109, 1988. 

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