Stepwise reactions photochemical

How can these photochemical and electrochemical data be reconciled With the benzylic molecules under discussion, electron transfer may involve the n or the cr orbital, giving rise to stepwise and concerted mechanisms, respectively. This is a typical case where the mechanism is a function of the driving force of the reaction, as evoked earlier. Since the photochemical reactions are strongly down-hill whereas the electrochemical reaction is slightly up-hill at low scan rate, the mechanism may change from stepwise in the first case to concerted in the second. However, regardless of the validity of this interpretation, it is important to address a more fundamental question, namely, whether it is true, from first principles, that a purely dissociative photoinduced electron transfer is necessarily endowed with a unity quantum yield and, more generally, to establish what are the expressions of the quantum yields for concerted and stepwise reactions. 

The easiest explanation is based on the frontier orbitals—the highest occupied molecular orbital (HOMO) of one component and the lowest unoccupied orbital (LUMO) of the other. Thus if we compare a [2 + 2] cycloaddition 6.133 with a [4 + 2] cycloaddition 6.134 and 6.135, we see that the former has frontier orbitals that do not match in sign at both ends, whereas the latter do, whichever way round, 6.134 or 6.135, we take the frontier orbitals. In the [2 + 2] reaction 6.133, the lobes on C-2 and C-2 are opposite in sign and represent a repulsion—an antibonding interaction. There is no barrier to formation of the bond between C-l and C-l, making stepwise reactions possible the barrier is only there if both bonds are trying to form at the same time. The [4 + 4] and [6 + 6] cycloadditions have the same problem, but the [4 + 2], [8 + 2] and [6 + 4] do not. Frontier orbitals also explain why the rules change so completely for photochemical reactions, as we shall see in Chapter 8. 

Photochemical Pericydic Reactions and Related Stepwise Reactions... 

Now are there such reactions as [2 + 2] cycloadditions Can, say, two molecules of ethylene combine to form cyclobutane The answer is yes, but not easily under thermal conditions. Under vigorous conditions cycloaddition may occur, but step-wise—via diradicals—and not in a concerted fashion. Photochemical [2 + 2] cycloadditions, on the other hand, are very common. (Although some of these, too, may be stepwise reactions, many are clearly concerted.)... 

According to the Woodward-Hoflfmann rules, concerted thermal [2+2] cycloadditions are symmetry-forbidden, but should proceed via supra-antarafacial attack of the reactants. [2+2] cycloadditions of ketenes and related reactive intermediates generated in situ proceed by a stepwise mechanism. " Photochemical [2+2] cycloadditions are symmetry-allowed. Asymmetric [2+2] cycloadditions leading to 4-membered heterocycles, e.g. Staudinger reactions or Patemo-BUchi reactions, have been extensively studied in the past. 

It has been noted that the excited states generated during the reaction could lead to side-reactions with other reagents, but this can be solved by adopting a stepwise reaction protocol in which iminium ions are generated photochemically to which are added nucleophiles in the absence of light, in a manner akin to some of the non-photochemical stepwise CDC-type reactions that have been reported. ... 

Moriyama, M., Sato, T., Uchimaru, T., and Yabe, A, Multi-step photolysis of benzenetetracarboxylic dianhydrides in low-temperature argon matrices exploration of reactive intermediates containing benzdiynes produced stepwise during photochemical reactions, Phys. Chem. Chem. Phys., 1, 2267, 1999. 

Using these characteristics of lasers, photochemical reactions that cannot be conducted with conventional Hght sources can be brought about, and a multiphoton reaction is one of these processes. Multiphoton reactions can be classified in two categories (1) stepwise reactions through short-lived transient species (Path 1 in Scheme 1) and (2) reactions by concerted multiphoton absorptions (Path 2 in Scheme 1). In many cases. Path 1 predominates when the substrates are complex organic compounds. The transient species can be either long-lived excited states, such as triplet states, or chemical species, such as radicals, carbenes, nitrenes, and thermally unstable molecules. 

Although the concerted mechanism described in the preceding paragraph is available only to those azo compounds with appropriate orbital arrangements, the nonconcerted mechanism occurs at low enough temperatures to be synthetically useful. The elimination can also be carried out photochemically. These reactions presumably occur by stepwise elimination of nitrogen, and the ease of decomposition depends on the stability of the radical R ... 

Nature, however, has performed more than simple stepwise transformations using a combination of enzymes in so-called multienzyme complexes, it performs multistep synthetic processes. A well-known example in this context is the biosynthesis of fatty acids. Thus, Nature can be quoted as the inventor of domino reactions. Usually, as has been described earlier in this book, domino processes are initiated by the application of an organic or inorganic reagent, or by thermal or photochemical treatment. The use of enzymes in a flask for initiating a domino reaction is a rather new development. One of the first examples for this type of reaction dates back to 1981 [3], although it should be noted that in 1976 a bio-triggered domino reaction was observed as an undesired side reaction by serendipity [4]. 

It is also worth emphasizing that recent theoretical work on photoinduced stepwise and concerted electron transfer/bond-breaking reactions opens the route to a more systematic combination than before of the electrochemical and photochemical approaches to the same problems. 

Nonradiative energy transfer has a major role in the process of photosynthesis. Light is absorbed by large numbers of chlorophyll molecules in light-harvesting antennae and energy is transferred in a stepwise manner to photosynthetic reaction centres, at which photochemical reactions occur. This fundamental energy-transfer process will be considered in more detail in Chapter 12. 

Eaton and co-workers also reported the synthesis of 1,3,5-trinitrocubane and 1,3,5,7-tetranitrocubane (39) ° The required tri- and tetra-substituted cubane precursors were initially prepared via stepwise substitution of the cubane core using amide functionality to permit ort/jo-lithiation of adjacent positions. The synthesis of precursors like cubane-1,3,5,7-tetracarboxylic acid was long and inefficient by this method and required the synthesis of toxic organomercury intermediates. Bashir-Hashemi reported an ingenious route to cubane-1,3,5,7-tetracarboxylic acid chloride (35) involving photochemical chlorocarbonylation of cubane carboxylic acid chloride (34) with a mercury lamp and excess oxalyl chloride. Under optimum conditions this reaction is reported to give a 70 8 22 isomeric mixture of 35 36 37... 

Treatment of the intermediate silylenolefher, obtained by reaction of 106 with CgQ, with SiOj and triethylamine leaves the methoxy group and yields a mixture of the two isomers 107 and 108 (Scheme 4.18) [99, 100], This reaction can be carried out either photochemically or thermally. Because the trans-product 107 is the major product under both thermal and photochemical conditions, the mechanism of this addition is concluded to proceed stepwise. The first step is probably an electron transfer from the Danishefsky diene to CgQ. At least for the photochemical pathway this electron-transfer step could be proven [100]. 

The reaction of a-diazocarbonyl compounds with nitriles produces 1,3-oxazoles under thermal (362,363) and photochemical (363) conditions. Catalysis by Lewis acids (364,365), or copper salts (366), and rhodium complexes (367) is usually much more effective. This latter transformation can be regarded as a formal [3 + 2] cycloaddition of the ketocarbene dipole across the C=N bond. More than likely, the reaction occurs in a stepwise manner. A nitrilium ylide (319) (Scheme 8.79) that undergoes 1,5-cyclization to form the 1,3-oxazole ring has been proposed as the key intermediate. 

Unlike thermal [2 + 2] cycloadditions which normally do not proceed readily unless certain structural features are present (see Section 1.3.1.1.), metal-catalyzed [2 + 2] cycloadditions should be allowed according to orbital symmetry conservation rules. There is now evidence that most metal-catalyzed [2 + 2] cycloadditions proceed stepwise via metallacycloalkanes as intermediates and both their formation and transformation are believed to occur by concerted processes. In many instances such reactions occur with high regioselectivity. Another mode for [2 + 2] cyclodimerization and cycloadditions involves radical cation intermediates (hole-catalyzed) obtained from oxidation of alkcnes by strong electron acceptors such as triarylammini-um radical cation salts.1 These reactions are similar to photochemical electron transfer (PET) initiated [2 + 2] cyclodimerization and cycloadditions in which an electron acceptor is used in the irradiation process.2 Because of the reversibility of these processes there is very little stereoselectivity observed in the cyclobutanes formed. 

A very rare example of preferential photochemical reduction of an a-C-F bond rather than a //-chlorine occurs with chlorofluoropropanoates, in which this unusual selection in radical reactions is achieved by photochemical reduction.107 In oc.oc-difluoro esters 6 both C-F bonds can be reduced stepwise using hexamethylphosphoric triamide as the solvent and hydrogen donor.108 100... 

In the thermal reaction the [4 + 2] or Diels-Alder adduct is the major product, whereas in the photochemical reaction [2 + 2] cycloadditions dominate. Because the photochemical additions are sensitized by a ketone, C6H5-COCH3, these cycloadditions occur through the triplet state of 1,3-butadiene and, as a result, it is not surprising that these cycloadditions are stepwise, nonstereospecific, and involve diradical intermediates. 

More detailed consideration of light absorption and consequent chemical changes is left to Chapter 13, but it is appropriate here to summarize briefly the types of compounds that are convenient photochemical radical sources. Many of the substances we have been discussing as thermal radical sources absorb light in the visible or ultraviolet and can be decomposed photochemically. The azoalkanes are particularly versatile they absorb around 350 nm and decompose cleanly to nitrogen and two radicals just as in the thermal reaction. As we have already noted, a preliminary photochemical isomerization to the cis isomer precedes the homolysis, which is actually a thermal decomposition of this unstable form.78 CIDNP observations confirm a stepwise decomposition pathway, and clarify the various reactions of the radicals produced.79... 

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. 

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