Head-to-tail-anti

It may be suspected that the genuinely topotactic (as secured by the molecular precision of the AFM [18]) photodimerization of 2-benzyl-5-benzyli-denecyclopentanone [118] might be a good candidate for a quantitative preparative photo dimerization to give the head-to-tail anti-[2+2] dimer. Early quantitative solid-state [2-1-2] photodimerizations (most of the published mechanistic interpretations of which can no longer be accepted) are listed in [110]. These deal with the anti dimerization of acenaphthylene-1,2-dicarboxylic anhydride, the head-to-head syn dimerization of acenaphthylene-1-carboxylic acid, the syn dimerization of 5,6-dichloroacenaphthylene, and the thermally reversible head-to-tail anti dimerization of seven ( )-2,6-di-f-butyl-4-(2-aryl-ethenyl)pyrylium-trifluoromethanesulfonates. All of these reactions proceed fully specific. On the other hand, quantitative photoconversions of a 1 1 mixed crystal of ethyl and propyl a-cyano-4-[2-(4-pyridyl)ethenyl]cinnamates gives mixtures of diesters with one (A>410 nm) or two cyclobutane rings (no cutoff filter). 

Keywords enone, photolysis, [2+2]-cycloaddition, head-to-tail-anti, cyclobutane, spiro compound... 

If two reactive groups are attached at 1,5-position [47], intramolecular photocycloaddition is restricted to a trans head-to-tail (anti) addition. Furthermore, the chain is now linked to a carbon which is involved in the reaction, [47]n=2 reacts faster than [47]n=3. 

The [2 + 2] photodimerization of a, j8-unsaturated sulfones is correctly viewed as a photoreaction of alkenes, rather than the sulfone group, and this aspect has been reviewed recently by Reid, as part of a wider survey of the photoreaction of O- and S-heterocycles. The topic continues to attract considerable interest and a few recent examples, as well as some synthetic applications, will be discussed here. Much of the photodimerization work has been carried out on the benzo[fc]thiophene (thianaphthene) 1,1-dioxide system. For example. Porter and coworkers have shown that both 3-carboxybenzo[i]thiophene 1,1-dioxide (65) and its methyl ester give only the head-to-head (hth), anti dimer (66) on irradiation in ethanol. In a rather unusual finding for such systems, the same dimer was obtained on thermal dimerization of 65. Similar findings for a much wider variety of 3-substituted benzo[fi]thiophene 1,1-dioxides have been reported more recently by Geneste and coworkers . In the 2-substituted analogs, the hth dimer is accompanied by some of the head-to-tail (htt), anti dimer. The formation of the major dimer appears to proceed by way of an excited triplet and the regiochemistry observed is in accord with frontier MO theory. 

Dimers (73) and (74) were formed in approximately equal amounts in all cases, although, as in the cases of 2-cyclopentenone and 2-cyclohexenone, the relative amount of (72) (either cis-syn-cis or cis-anti-cis) was found to vary substantially with solvent polarity. As in 2-cyclopentenone, this increase in the rate of head-to-head dimerization was attributed to stabilization of the increase in dipole moment in going to the transition state leading to (72) in polar solvents. It is thought that the solvent effect in this case is not associated with the state of aggregation since a plot of Stem-Volmer plot and complete quenching with 0.2 M piperylene indicate that the reaction proceeds mainly from the triplet manifold. However, the rates of formation of head-to-head and head-to-tail dimers do not show the same relationship when sensitized by benzophenone as in the direct photolysis. This effect, when combined with different intercepts for head-to-head and head-to-tail dimerizations quenched by piperylene in the Stem-Volmer plot, indicates that two distinct excited triplet states are involved with differing efficiencies of population. The nature of these two triplets has not been disclosed. 

With two y,8 double bonds, two a,/3 double bonds, and the possibilities of cis and trans ring fusions with syn and anti configurations, 20 isomeric dimers are possible. Surprisingly, only one product is formed in a head-to-tail fashion. The sole product of the irradiation of the 3,5-diene-7-ketosteroid (76), however, is the head-to-head dimer. The specificity and mode of addition arise presumably through the effect of the specific environment of the chromaphore. The dimerization of (75) is believed to involve the addition of the a,fi double bond of a photoexcited molecule to the less hindered y,8 double bond of a ground state molecule. The photocondensation of (76) with cyclopentene, in which steric hindrance should not be a controlling factor, was found to yield a cyclobutane product involving the a,/ bond of the steroid in contrast to dimerization across the y,8 bond. 

Theoretically, trans-p-coumaric acid can produce 12 isomers depending on whether head-to-tail (4,4 -dihydroxytruxillic acid) or head-to-head (4,4 -dihydroxytruxinic acid) dimerizations occur with syn or anti and with cis or trans ring junctions (37). Mass spectrometric analysis of the tetra-TMSi derivatives showed that head-to-tail dimers split symmetrically on electron impact, whereas head-to-head dimers fragment asymmetrically (Figures 2 and 3) (33,35,38,39). Thus the tetra-TMSi derivative of 4,4 -dihydroxytruxillic acid has a mass spectrum similar to that of the bis-TMSi derivative of p-coumaric acid (33). 

Under the standard conditions, alternating copolymerization is initiated by the insertion of propene to the Pd-carbon bond of Pd(COOMe) species. Addition of a large amount of an oxidant results in shortening the copolymer chain, that is, inhibiting propagation. Thus, with this protocol, dimers were prepared to estimate the enantiopurity of the chiral centers in the polymer main chain [131). For example, a head-to-tail and anti-dimer with >98% ee was obtained in the reaction catalyzed by a cationic Pd-[MeO-BICHEP] complex with 85% selectivity over other diastereomers (Scheme 7.13). 

Stereoselectivity. The SCF can influence the stereoselectivity as well as the regioselectivity of a cyclic enone dimerization. There are both syn and anti stereoisomers of the head-to-tail dimers of both isophorone and cyclohexenone. The differences in alignment of the cyclohexyl rings was portrayed schematically by Hrnjez et al. (31). Both HT photodimers for isophorone have similar dipole moments. Hence, a variation in solvent polarity is not expected to influence the anti/syn ratio and, indeed, these stereoisomers are formed in equal amounts regardless of the dielectric constant in liquid solvents (32). For the cyclohexenone HT stereoisomers, the anti configuration dominates in acetonitrile and benzene, but there has been limited study of stereoselectivity in other liquids. 

Four-membered rings can be synthesised by [2 + 2] cycloadditions. However, thermal [2 + 2] cycloadditions occur only with difficulty they are not concerted but involve diradicals. Photochemical [2 + 2] reactions are common and although some of these may occur by a stepwise mechanism many are concerted. An example of a [2 + 2] reaction is the photodimerisation of cyclopent-2-enone. This compound, as the neat liquid, or in a variety of solvents, on irradiation with light of wavelength greater than 300 nm (the n - n excited state is involved) is converted to a mixture of the head-to-head (48) and head-to-tail (49) dimers, both having the cis,anti,cis stereochemistry as shown. It is believed that the reaction proceeds by attack of an n - n triplet excited species on a ground state molecule of the unsaturated ketone (Section 2.17.5, p. 106). In the reaction described (Expt 7.24) the cyclopent-2-enone is irradiated in methanol and the head-to-tail dimer further reacts with the solvent to form the di-acetal which conveniently crystallises from the reaction medium as the irradiation proceeds the other dimer (the minor product under these conditions) remains in solution. The di-acetal is converted to the diketone by treatment with the two-phase dilute hydrochloric acid-dichloromethane system. 

Figure 9.9. [2 + 2] photodimerization pathways within the LDH interlayer. Simplified drawing of anti-parallel packing of (a) />-phenylcinnamate and (b) stilbenecarboxylate anions (SBC), (c) Effect of coadsorbate, />-phenylbenzoate (PEB), on product selectiv-ities of intercalated SBC in water. A formation of head-to-head dimers. B formation of head-to-tail dimers. C isomerization to cis-SBC. After Sasai et al. [110]. 

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