1,3,5-hexatrienes electrocyclization

Correlation diagrams can be constructed in an analogous fashion for the disrotatory and conrotatory modes for interconversion of hexatriene and cyclohexadiene. They lead to the prediction that the disrotatory mode is an allowed process whereas the conrotatory reaction is forbidden. This is in agreement with the experimental results on this reaction. Other electrocyclizations can be analyzed by the same method. Substituted derivatives of polyenes obey the orbital symmetry rules, even in cases in which the substitution pattern does not correspond in symmetiy to the orbital system. It is the symmetry of the participating orbitals, not of the molecule as a whole, that is crucial to the analysis. 

The prediction on the basis of orbital symmetry analysis that cyclization of eight-n-electron systems will be connotatoiy has been confirmed by study of isomeric 2,4,6,8-decatetraenes. Electrocyclic reaction occurs near room temperature and establishes an equilibrium that favors the cyclooctatriene product. At slightly more elevated temperatures, the hexatriene system undergoes a subsequent disrotatory cyclization, establishing equilibrium with the corresponding bicyclo[4.2.0]octa-2,4-diene ... 

The cyclohexadiene-hexatriene system seems to be less complicated than the cyclobutene-butadiene system. Cyclohexadiene undergoes photochemical electrocyclic ring opening ... 

Electrocyclic reaction (Section 30.3) A unimolecular peri-cyclic reaction in which a ring is formed or broken by a concerted reorganization of electrons through a cyclic transition state. For example, the cyciization of 1,3.5-hexatriene to yield 1,3-cyclohexadiene is an electrocyclic reaction. 

In the transition state of the electrocyclization of (Z)-l,3,5-hexatriene to 1,3-cyclohexadiene (Scheme 22 entry 1) a new six-membered ring develops analogously... 

J. Rimmelin and G. Jenner, Tetrahedron, 30, 3081 (1974). A recent measurement of the pressure and temperature dependence of die electrocyclic ring-closure of Z-l,3,5-hexatriene to 1,3-cyclohexadiene in the range of 200 to 2500 bar and 100 to 125 °C does not show a significant temperature dependence of die activation volume (M. K. Diedrich and F. -G. Klarner, unpublished results). 

Although a few other acyclic examples of stereospecific isomerisation of hexatrienes are known, specially in the field of natural product like steroid chemistry, the commonest reactions of this type are in cyclic hexatrienes. Cyclooctatriene and cyclooctatetraene are systems in which the electrocyclic reaction goes very readily and they show an interesting trend. 

Deprotonation of Cl gives an enolate ion, which in this compound is actually a 1,3,5-hexatriene. As such it can undergo an electrocyclic ring closing. Protonation gives the product. 

It should be noted that products like 443 and 447 are the normal products of photochemical reactions of acyclic 1,3,5-hexatrienes, as well as of divinyl aromatics, but are quite unusual for thermal transformations of such substrates. Presumably, the electrostatic repulsion between CF2 groups prevents the formation of conformation 450 which is necessary for the electrocyclic ring closure (i.e. 438 — 439 and 445 -> 446). Instead, it leads to conformation 451 which is favorable to generate the diradical and then the fused vinyl-cyclopropane intermediates 452 (equation 170). Note that the rearrangement 452 —> 453... 

The acyclic fluorinated 1,3,5-hexatriene system 454 is also resistant to 6 r-electron electrocyclic ring closure at temperatures up to 200 °C while the analogous hydrocarbons cyclize easily at 160 °C (equation 171)232. 

The (diphenylmethylene)aminocyclobutenecarboxylates 109 obtained by rearrangement of the DMPA-H adducts of 1-Me, 2-Me, contain a 2-azadiene unit and a cyclobutene moiety. Indeed, the parent compound 109 a reacted with 4-phenyl-l,2,4-triazoline-3,5-dione (PTAD, [80]) at room temperature in a [4-1-2] cycloaddition mode to yield the tricyclic tetraazaundecene 132 in almost quantitative yield (Scheme 44) [8]. As substituted cyclobutenes, compounds 109 should be capable of opening up to the corresponding butadienes [1, 2b, 811. When compounds 109 were subjected to flash vacuum pyrolysis, the dihydro-isoquinolines 135 were obtained, presumably via the expected ring-opened intermediates 133, which subsequently underwent bn electrocyclization followed by a 1,5-shift, as is common for other 3-aza-l,3,5-hexatrienes [82]. 

A still more demanding ultrafast electron diffraction study of the electrocyclic ring-opening isomerization of 1,3-cyclohexadiene to l,3(Z),5-hexatriene was... 

Figure 14.3. (a) Orbital correlation diagram for electrocyclic reaction of butadienes (b) Orbital correlation diagram for electrocyclic reaction of hexatrienes. Solid lines and S, A denote correlation for conrotatory motion dashed lines and S, A denote correlation for disrotatory motion. 

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