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• W1991988511 abstract "The mechanistic aspects of the photosensitized reactions of a series of oxime ethers were studied by steady-state (product studies) and laser flash photolysis methods. Nanosecond laser flash photolysis studies have shown that chloranil-sensitized reactions of the oxime ethers result in the formation of the corresponding radical cations. The radical cation species react with nucleophiles such as MeOH by clean second-order kinetics with rate constants of (0.7−1.4) × 106 M-1 s-1. Only a small steric effect is observed in these reactions, which is taken as an indication that the reaction center is not the O-alkyl moiety, but rather somewhere else in the molecule. Product studies in a polar nonnucleophilic solvent (MeCN) revealed that in order for the oxime ether radical cation to react more readily, α-protons must be available on the alkyl group. The O-methyl (1), O-ethyl (2), and O-benzyl (3) acetophenone oximes all reacted readily to give acetophenone oxime as the major product (as well as an aldehyde derived from the O-alkyl group), whereas O-tert-butyl acetophenone oxime (4) did not. The product formation can be explained by a mechanism that involves electron transfer followed by proton transfer (α to the oxygen) and subsequent β-cleavage. When using 3 in MeOH, a change in the product formation is observed, the most important difference being the presence of benzyl alcohol rather than benzaldehyde as the major product. On the basis of the data from LFP and steady-state experiments, it is suggested that the competing mechanism under these conditions involves electron transfer, followed by a nucleophilic attack on the nitrogen, a MeOH-assisted [1,3]-proton transfer, and subsequent loss of benzyl alcohol. This mechanism is supported by DFT (B3LYP/6-31G*) and AM1 calculations." @default.
• W1991988511 created "2016-06-24" @default.
• W1991988511 creator A5026960977 @default.
• W1991988511 creator A5083886440 @default.
• W1991988511 date "2004-04-01" @default.
• W1991988511 modified "2023-09-23" @default.
• W1991988511 title "Photosensitized Reactions of Oxime Ethers: A Steady-State and Laser Flash Photolysis Study" @default.
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• W1991988511 doi "https://doi.org/10.1021/jo049941a" @default.
• W1991988511 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/15104444" @default.
• W1991988511 hasPublicationYear "2004" @default.
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