Photochemically allowed conversions

Intramolecular photodimerization of 2-pyridones provides a series of primary photoproducts, the structures of which were a function of the chain length comecting the two reactive centers." The initially formed dimers were characterized as being derived from a photochemically allowed [2 + 2] cycloaddition process in each case examined. A particularly interesting example from this study in terms of [4 + 4] cycloaddition chemistry is the conversion of dipyridone (114) into Ae net [4 + 4] dimer (115) via a facile thermal rearrangement. " Further irradiation of the [4 + 4] species (115) produced a second [2 + 2] adduct that was isomeric with the initially formed metastable species. 

Pd-C, or iodine/ " The reaction is a photochemically allowed conrotatory conversion of a 1,3,5-hexatriene to a cyclohexadiene, followed by removal of two hydrogen atoms by the oxidizing agent. The intermediate dihydrophenanthrene has been isolated. The use of substrates containing heteroatoms (e.g., PhN=NPh) allows the formation of heterocyclic ring systems. The actual reacting species must be the c/i-stilbene, but frani-stilbenes can often be used, because they are isomerized to the cis isomers under the reaction conditions. The reaction can be extended to the preparation of many fused aromatic systems, for example, ... 

The hexatriene/cyclohexadiene isomerization has been extensively studied and has been the topic of numerous reviews and monographs this section will attempt to deal only with applications of these reactions to synthesis, and in particular the use of these reactions for the synthesis of natural products. Much of the early work in this area was done by Havinga and coworkers during the course of their detailed work on the stereochemical consequences of the thermal and photochemical conversions in the vitamin D field this work provided much of the impetus for the development and elaboration of the Woodward-Hoffman mles (Scheme 7). The reversible photochemical ring opening of provitamin 30 to precalciferol (31) and the photochemical ring closure of 31 to lumisterol 32 can be explained by consecutive photochemically allowed conrotatory processes. ... 

Two variants of this rearrangement have been reported. One uses triethyl phosphite instead of diethyl chlorophosphite. Thus, in the presence of a catalytic amount of para-toluenesulfonic acid, triethyl phosphite reacts with propargyl alcohol in DMF at room temperature to give a mixture of diethyl allenylphosphonate (51%) and diethyl 1-propynylphosphonate (14%). The second variant is based on the conversion of dialkyl allenylphosphonates (R , R H, R = H, Scheme 1.19) into dialkyl 1-alkynylphosphonates by a photochemically allowed [l,3s]-sigmatropic shift in ( ,11, with 46-50% yields. ... 

Sigmatropic reactions of order [/, ] are thermally allowed to be suprafacial— suprafacial or antarafacial-antarafacial and are photochemically allowed to be antarafacial-suprafacial or suprafacial- antarafacial if i + j = 4n + 2. Conversely, they are thermally allowed to be antarafacial- suprafacial or suprafacial-antarafacial and photochemically allowed to be suprafacial-suprafacial or antarafacial-antarafacial if i + j=4n. 

The i j -configuration of the 6,7-double bond in pre-vitamin D is critical to its subsequent thermal rearrangement to the active vitamin. A photochemical isomerization of pre-vitamin D to yield the inactive trans-isoTnen occurs under conditions of synthesis, and is especially detrimental if there is a significant short wavelength component, eg, 254 nm, to the radiation continuum used to effect the synthesis. This side reaction reduces overall yield of the process and limits conversion yields to ca 60% (71). Photochemical reconversion of the inactive side product, tachysterol, to pre-vitamin D allows recovery of the product which would otherwise be lost, and improves economics of the overall process (70). 

In the photochemical isomerization of isoxazoles, we have evidence for the presence of the azirine as the intermediate of this reaction. The azirine is stable and it is the actual first photoproduct of the reaction, as in the reaction of r-butylfuran derivatives. The fact that it is able to interconvert both photochemically and thermally into the oxazole could be an accident. In the case of 3,5-diphenylisoxazole, the cleavage of the O—N bond should be nearly concerted with N—C4 bond formation (8IBCJ1293) nevertheless, the formation of the biradical intermediate cannot be excluded. The results of calculations are in agreement with the formation of the azirine [9911(50)1115]. The excited singlet state can convert into a Dewar isomer or into the triplet state. The conversion into the triplet state is favored, allowing the formation of the biradical intermediate. The same results [99H(50)1115] were obtained using as substrate 3-phenyl-5-methylisoxazole (68ACR353) and... 

CgoO (1) can also be prepared by allowing toluene solutions of CgQ to react with dimethyldioxirane (Scheme 8.3) [28], The so-obtained product is identical to that prepared by photochemical epoxidation [15], Upon treatment of CgQ with dimethyldioxirane, a second product is formed simultaneously (Scheme 8.3), which was identified to be the 1,3-dioxolane 6. Upon heating 6 in toluene for 24 h at 110 °C, no decomposition could be observed by HPLC, implying that 1 and 6 are formed by different pathways. Replacement of dimethyldioxirane with the more reactive methyl(trifluoromethyl)dioxirane allows much milder reaction conditions [29]. At 0 °C and a reaction time of only some minutes this reaction renders a CgQ conversion rate of more than 90% and higher yields for CgoO as well as for the higher oxides. 

The procedure developed in the initial NMR study of 12 has been used in subsequent studies of 61, 62 ° of 41 and 44 of and of 64 The DHP derivative can be obtained only in photostationary concentrations (at most), in reaction mixtures containing both cis- and trans-isomers of the 1,2-diaryl ethylene. Under such conditions the NMR signals due to the nuclei of the DHP derivative are identified as those which disappear following photochemical ring cleavage (process B). This process yields only the cis-isomer of the parent ethylenic compound. In addition to their structural value, NMR studies in this field allow to verify the conversion estimates obtained from optical studies In 61, 62 and 64 proton NMR proves that photocyclization takes place between 1 and 1 atoms and not for instance between atoms 1 and 8 or between atoms 8 and 8 (numbering as in 61 in Table 8). Table 10 provides a summary of the chemical shifts of 12, 25, 41, 44, 61, 62, and 64. The atoms of the DHP moiety are numbered as in 7 (see Tables 1—9 for details). 

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