Alkene oxidation, photo

Steroids Carbonyl Compounds Cycloaddition Enone and Dienone Rearrangements Alkenes Isomerisation and Rearrangement Alkenes Cycloaddition Alkenes Photo-oxidation Terpenoids Aromatic Compounds Isomerisation and Cycloaddition Practical Photochemistry Scale-up Aromatic Compounds Substitution and Cyclisation Alkaloids Photoinitiated Free-radical Chain Reactions. 

Pfbrtner, K.H., Alkenes photo-oxidation, in Photochemistry in Organic Synthesis, Coyle, J.D., Ed., Special pubHcation, The Royal Society of Chemistry, 57,189,1986. 

In 1999, Clennan and Sram reported a study of the photo-oxidations of a series of tetrasubstituted alkenes (Fig. 5) in methylene blue-doped zeolite Y [11], The ene regiochemistries are very sensitive to the size of the allylic substituent, R, in solution. The A/B ratio increases from 0.49 to 2.4 as the substituent, R, is changed from methyl to ferr-butyl. This phenomenon has been attributed [12] to a sterically induced lengthening of the carbon-2 oxygen bond in the perepoxide intermediate I and subsequent preferred opening of this long bond (Fig. 5). 

These intrazeolite singlet oxygen ene reactions have synthetic potential because the cis effect observed in solution is suppressed in the zeolite [13]. Consequently, allylic hydroperoxides which are inaccessible by other routes may be available via this new technology. For example, photo-oxidations of aryl-substituted alkenes, 7, in sensitizer-doped NaY react to generate the allylic hydroperoxides as the major or exclusive product [17]. In contrast, in solution, the hydroperoxides are formed in only 5-20% yields, with 2-1-2 and 4-1-2 adducts dominating the reaction mixtures. In the case of 2-methyl-5-phenyl-2-hexene, 8, the regio-selectivity for 8b and 8c improved from 47% to 94% and the diastereoselectivity from 10% to 44% as the reaction is moved from solution into the zeolite [18] ... 

In 1993, Blatter and Frei [34] extended the Aronovitch and Mazur [28] photo-oxidation into zeolitic media, which resulted in several distinctive advantages as described below. Irradiation in the visible region (633 nm) of zeolite NaY loaded with 2,3-dimethyl-2-butene, 16, and oxygen resulted in formation of allylic hydroperoxide, 17, and a small amount of acetone. The reaction was followed by in situ Fourier-transform infrared (FTlR) spectroscopy and the products were identified by comparison to authentic samples. The allylic hydroperoxide was stable at - 50°C but decomposed when the zeolite sample was warmed to 20°C [35]. In order to rationalize these observations, it was suggested that absorption of light by an alkene/Oi charge-transfer complex resulted in electron transfer to give an alkene radical cation-superoxide ion pair which collapses... 

An extremely interesting feature of these mechanisms is the fact that superoxide and the alkene radical cation are both formed in the reduction (Fig. 20) and also in the Frei oxidation (Fig. 19). In the Frei photo-oxidation, however, they are formed concurrently in a tight ion pair and collapse to product more rapidly than their diffusive separation. In the reduction (Fig. 20), the formation of the radical cation and superoxide occur in independent spatially separated events allowing the unimpeded diffusion of superoxide which precludes back-electron transfer (BET) and formation of oxidized products. The nongeminate formation of these two reactive species provides the time necessary for the radical cation to abstract a hydrogen atom from the solvent on its way to the reduced product. 

The 02 ion appears to play an important role in a number of photooxidation reactions (see Section VI,C) for example, the photo-oxidation of alkenes over TiOz. However, it seems likely that OJ is not, in many cases, active in the oxidation step but further conversion occurs to give a mononuclear species, not detected directly, which then oxidizes the adsorbed hydrocarbons. Photo-oxidation of lattice oxygen in the M=0 systems (e.g., V2Os supported on PVG) gives rise to an excited charge transfer state such as V4 + -0 . This excited state can react as O- either by addition to a reactant molecule or by an abstraction reaction (see Section V of Ref. /). In the presence of oxygen, 03 is formed which then reacts further with organic molecules. 

In this section we will discuss photochemical synthesis of macrocycle, photoini-tiated oxidation of alkenes, photo-Fries rearrangement, photocycloaddition and chiral photochemical synthesis within a number of microreactors. 

Also, intermediate peroxides are formed in the oxidation of perfluorinated alkenes, e.g. in the photo-oxidation of perfluoroethene and perfluoropropene for the formation of Fomblin (Ausimont Co.) perfluoro-polyether fluids [198, 199]. 

A number of other photo-oxidations involving aromatic substrates have been reported, some of which again have been carried out in non-traditional reaction environments. A light-promoted oxidative cleavage of the olefinic bond in aromatic alkenes, which takes place in mesoporous Si02 (FSM 16) and involves a catalytic amount of I2, has been reported (Scheme 23). The photochemical involvement appears to extend no further than the formation of the iodine atoms. The suggestion that an a-iodoketone is an intermediate in the process is based on NMR evidence from the reaction where R = Bu, but it is not clear how this intermediate is converted to the final product. A similar transformation of aromatic alkenes has been carried out in zeolite NaY. Irradiation of styrene,... 

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