Tricyclo ring

In some cases the nature of the products resulting from photolysis of dienes and trienes depends on whether the reaction occurs from the excited singlet state or the triplet state. The triplet states can be populated exclusively by suitable sensitizers. For example, 3-methylene-1, 5-hexadiene gives a cyclobutene derivative (A) from the singlet state and tricyclo ring compound (B) from triplet state ... 

The extension to polycycles with three or more rings is straightforward prefixes tricyclo-, tetracyclo-, etc. are used and the positions of the additional bridges are specified by superscripts (examples 59-61). 

Fig. 9.3. (A) Carbon framework from X-ray crystal stmcture of iyn-tricyclo[8.4.1.1]hexadeca-1,3,5,7,9,11,13-heptaene. (B) Side view showing deviation from planarity of aimulene ring. (Reproduced from Ref 60 by permission from the International Union of Crystallography.)...

The factors influencing ring size and conformation have not yet become clear. Thus, the yellow (MeAs)5 has a puckered Asj ring with As-As 243 pm and angle As-As-As 102° there is also a more stable red form. (PhAs)6 has a puckered Asg (chair form) with As-As 246 pm and angle As-As-As 91°. Numerous polycyclic compounds As R have also been characterized, for example the bright-yellow crystalline tricyclo-... 

In Method 2, described by Rule A-31, the saturated cyclic parent is named as a polycyclo-[.. jalkane. The alkane name identifies the total number of carbon atoms in the ring system. The names bicyclo, tricyclo, tetracyclo, etc. identify parent compounds of two, three, four, etc. rings. Double bonds in the ring are identified by names such as w-alkenc, ,/w-alkadicne, where the n and m give the position of the double bond. Substituents consist of alkyl, cycloalkyl, phenyl, etc. radicals. 

The di-rc-methane rearrangement is also a convenient way of obtaining polycyclic fused ring systems as illustrated in the synthesis of a tricyclo-undecane (3.17) 327). In the irradiation of dihydrotriquinacene the initial bonding scheme is identical as in (3.14) but ultimate cyclopropane formation is hindered by structural reasons (3.18) 328). 

The structures of [2]ladderane and [3]ladderane were determined by electron diffraction.22,23 Each cyclobutane ring of bicyclo[2.2.0]hexane has a folded structure with fold angle 11.5°, and the molecule has C2 symmetry.22 Anti- and yy/7-tricyclo[4.2.0.02,5]octanes also have folded cyclobutane rings with fold angles of 8.0 and 9.0°, respectively.23 MM2 calculations on... 

The thermolysis of ladderanes has been studied in detail (Scheme 1). On heating, bicyclo[2.2.0]hexane and its derivatives exhibit skeletal inversion and cleavage to 1,5-hexadiene derivatives.26 The thermolysis of anti- and yyft-tricyclo[4.2.0.02,5]octanes and their derivatives gives cis,cis- and cis, trans-1,5-cyclooctadienes, cis- and trans-1,2-divinylcy clobutanes, and 4-vinylcyclohexene as ring-opening products.27-29 Furthermore, syn-tricyclo-[4.2.0.02,5]octane isomerizes to aw//-tricyclo[4.2.0.02,5]octane.29c,d The thermodynamic parameters and the reaction mechanisms for these thermal reactions have been discussed. 

The structure of polynorbornadiene [poly(3,5-tricyclo(2.2.1.02 6]heptylene] (5) [28] and the high level of incorporation suggest that the three-membered rings in the polymer behave like double bonds and have been aluminated. 

A solid-state transformation that involves an electrocyclic ring opening is described by Bellus and his co-workers (78). They found that when 1,2,5,6-tetracyano-anri-tricyclo-[4.2.0. O Joctane (33) is heated in the crystal, only 1,2,5,6,-tetracyano-(Z,E)-cycloocta-l, 5-diene (34a) is formed, as expected on... 

Bicyclo[2.2.1]hept-2-enes react with p-bromostyrene to form 1 2 adducts 2-(phenylethynyl)-3-(2-phenylethenyl)bicyclo[2.2.1]heptane and the ring-closed tricyclo compound are both isolated (Scheme 6.32) [45]. Comparison of these results should be with those of the reaction in the absence of the quaternary ammonium salt, where the major reaction pathway leads to 2 1 and 1 1 adducts [46]. 

XII. Tricyclic Systems Containing a Cyclobxttane Ring The only system of this kind which appears to have been investigated kinetically in detail is tricyclo[3,3,0,0 ]octane (Srinivasan and Levi, 1964). At temperatures in the range 327 to 366° C the isomerization is a homogeneous first-order reaction. The observed products were 4-vinyl-cyclohexene, butadiene and 1,5-cyclo-octadiene. However, from separate studies on the cyclo-octadiene, it is concluded that the tricyclo-octane first isomerizes to the cyclo-octadiene which then undergoes secondary reactions to yield the other observed products. The observed rate is then the rate of this primaiy reaction, viz. ... 

The regioselectivity in ketyl-radical-promoted ring cleavage of configurationally restricted tricyclo[3.3.0.0 ]octanone derivatives was investigated by Maiti and Lahiri, revealing new and additional information for this class of compounds in contrast to simple and unrestrained cyclopropyl ketones [9],... 

The Michael addition followed by Intramolecular Ring Closure (MIRC) reactions have been recognized as a general synthetic approach to carbocyclic three-membered ring derivatives [1]. The enhanced Michael reactivity of methyl 2-chloro-2-cyclopropylideneacetate (1-Me) towards thiolates, alkoxides, lithiated amides and cyclohexadienolates (see below) allows one to perform highly efficient assemblies of spiropentane, tricyclo [3.2.1.0 ]octane, bicyclo [2.2.2] octane... 

Several 1,4-disubstituted derivatives of the dication, 63, were successfully prepared. The 1,4-diphenyl, 1,4-dimethyl, 1,4-dicyclopropyl-substituted derivatives of carbodication 63 (65, 66, and 67) are exceptionally stable. The 1,4-dimethyl-1,4-cyclohexyl dication, devoid of the adjacent cyclopropyl groups, could not be prepared. The carbocationic center in all these dications are somewhat shielded as compared to their monocations. The C NMR chemical shifts of the carbocationic centers for the dications 65, 66, and 67 are 235.4, 293.4, and 260.8 ppm, respectively. The diprotonated ann -tricyclo(5.1.0.0 )octa-2,6-dione, 68, may be treated as a dicarboxonium ion, instead of dihydroxy dicarbenium ion, since the cabronyl carbon is shielded by only 25.2 ppm, much smaller than that observed for the protonated cyclohexanedione (34 ppm). The para carbons of the phenyl substituents in carbodication 65 are relatively shielded by about 5 ppm from that of the parent l,4-diphenylcyclohexane-l,4-diyl dication showing relatively less delocalization of the charge into the aromatic rings. 

The Cj - and 54-symmetric tetraesters of tricyclo[3.3.0.0 ]octane (430 and 431) have been prepared by oxidation of diene 429 To access the parent hydrocarbon (435), acid chloride 432 was transformed to the derived ketene which undergoes intramolecular [2+2] cycloaddition The resulting cyclobutanone (433) serves as precursor to perester 434 whose thermal decomposition proceeds with chain transfer in competition with cleavage The unique arrangement of the carbon atoms in 435 is such that the smallest rings are all five-membered. The highly symmetric structure may be viewed as a constrained cisoid bicyclo[3.3.0]octane (as well as the symbol of NATO). 

The first naturally occurring tricyclo[6.3.0.0 ]undecane to be synthesized was isocomene (757), a colorless oily sesquiterpene hydrocarbon isolated from several plant sources. In 1979, Paquette and Han reported an efficient, stereospecific approach starting with a preformed bicyclic enone, to which the third five-membered ring was appended with proper attention to stereochemistry and position of unsaturation (Scheme LXXX) The pivotal steps are seen to be the stannic chloride-induced cyclization of aldehyde 732 and the conjugate addition of lithium dimethylcuprate to 733 which sets the stereochemistry of the last methyl group. 

This method constitutes a convenient synthesis of substituted tricyclo[2.2.0.02,6]hexane derivatives. It is surprising that the ring strain associated with these derivatives would permit their preparation at such high temperatures. A homologous reaction involves the intramolecular [2 + 2] cycloaddition of 2-vinylphenyl substituted cyclopropenes 5 which give benzotricy-clo[3.2,0.02,7]heptenes 6.74 This reaction also proceeds by sensitized photolysis but gives a more complex mixture. 

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