Cyclobutene-diene interconversion, orbital

If the motion had been disrotatory, this would still have been evidence for a cyclic mechanism. If the mechanism were a diradical or some other kind of noncyclic process, it is likely that no stereospecificity of either kind would have been observed. The reverse reaction is also conrotatory. In contrast, the photochemical cyclobutene—1,3-diene interconversion is disrotatory in either direction.368 On the other hand, the cyclohexadiene—1,3,5-triene interconversion shows precisely the opposite behavior. The thermal process is disrotatory, while the photochemical process is conrotatory (in either direction). These startling results are a consequence of the symmetry rules mentioned in Chapter 15 (p. 846).Vl,As in the case of cycloaddition reactions, we will use the frontier-orbital and Mdbius-HQckel approaches.37"... 

This time it is conrotatory movement that results in a bonding situation, and formation of the trans dimethylcyclobutene (18). For the photochemical interconversion (which tends to lie over in favour of the cyclobutene), irradiation of the diene will result in the promotion of an electron into the orbital of next higher energy level, i.e. 3, and the HOMO to be considered now therefore becomes i/r3 (23) ... 

How can we account for the stereoselectivity of thermal electrocyclic reactions Our problem is to understand why it is that concerted 4n electro-cyclic rearrangements are conrotatory, whereas the corresponding 4n + 2 processes are disrotatory. From what has been said previously, we can expect that the conrotatory processes are related to the Mobius molecular orbitals and the disrotatory processes are related to Hiickel molecular orbitals. Let us see why this is so. Consider the electrocyclic interconversion of a 1,3-diene and a cyclobutene. In this case, the Hiickel transition state one having an... 

Fig. 18.4. The 1,3-diene-cyclobutene interconversion. The orbitals shown are not molecular orbitals, but a basis set of p-atomic orbitals, (a) Disrotatory ring closure gives zero sign inversion, (b) Conrotatory ring closure gives one sign inversion. We could have chosen to show any other basis set (e.g., another basis set would have two plus lobes above the plane and two below, etc.). This would change the number of sign inversion, but the disrotatory mode would stiU have an even number of sign inversions, and the conrotatory mode an odd number, whichever basis set was chosen.

FIGURE 20.9 In the interconversion of cyclobutene and butadiene, the orbitals at the end of the diene must rotate so as to form a bond, not an antibond. 

An electrocyclic reaction is as easy to analyze as that. Identify the HOMO, and then see whether conrotatory or disrotatory motion is demanded of the end carbons by the lobes of that molecular orbital. All electrocyclic reactions can be understood in this same simple way. The theory tells us that the thermal interconversion of cyclobutene and 1,3-butadiene must take place in a conrotatory way. For the cyclobutene studied by Vogel, conrotation requires the stereochemical relationship that he observed. The cis 3,4-disubstituted cyclobutene can only open in conrotatory fashion, and conrotation forces the formation of the cis,trans diene. Note that there are always two possible conrotatory modes (Fig. 20.12), either one giving the same product in this case. 

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