Exploration of photochemical reactions of N-trimethylsilylmethyl-substituted uracil, pyridone, and pyrrolidone derivatives

Title
Exploration of photochemical reactions of N-trimethylsilylmethyl-substituted uracil, pyridone, and pyrrolidone derivatives
Author(s)
조대원이찬우[이찬우]박종구[박종구]오선화[오선화]박혜정[박혜정]성남경[성남경]김경목[김경목]Patrick S. Mariano[Patrick S. Mariano]윤웅찬[윤웅찬]
Keywords
YLIDE-FORMING PHOTOREACTIONS; ELECTRON-TRANSFER MECHANISMS; DNA PHOTOLYASE; PHOTOCYCLIZATION REACTIONS; PHOTOADDITION REACTIONS; FUSED IMIDAZOLIDINES; DESILYLATION METHOD; IMINIUM SALTS; PHTHALIMIDE; SYSTEMS
Issue Date
201107
Publisher
ROYAL SOC CHEMISTRY
Citation
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, v.10, no.7, pp.1169 - 1180
Abstract
Photochemical reactions of N-trimethylsilylmethyl-substituted uracil, pyridone and pyrrolidone derivatives were carried out to determine if silicone containing substituents have an impact on excited state reaction profiles. The results show that ultraviolet irradiation of N-trimethylsilylmethyl substituted uracils in the presence of substituted alkenes leads to efficient formation of both dimeric and cross [2+2]-cycloaddition products. Qualitatively similar observations were made in a study of the photochemistry of N-trimethylsilylmethyl-2-pyridone. The combined results demonstrate that [2+2]-photocycloaddition is a more efficient excited state reaction pathway for the uracil and pyridone substrates as compared to other processes, such as ylide-forming trimethylsilyl group C-to-O migration. Finally, photoreactions of N-trimethylsilylmethyl-2-pyrrolidone in solutions containing dipolarophiles, such as methyl acrylate, lead to the formation of the desilylation product, N-methyl-2-pyrrolidone by way of a simple, non-ylide generating, protodesilylation process. In addition, observations were made which show that orbital symmetry allowed photocycloreversion reactions of dimeric uracil derivatives, involving cyclobutane ring splitting, to take place. These processes, which lead to the formation of monomeric uracils, appear to be stimulated by the presence of electron donor groups on the cyclobutane ring, a likely result of a new SET promoted cyclobutane ring cleavage pathway. In the cases of N-trimethylsilylmethyl-substituted cyclobutane derivatives that possess phthalimide groups, highly efficient excited state cleavage of the cyclobutane moiety occurs to produce uracil derivatives and corresponding vinyl phthalimide.
URI
http://hdl.handle.net/YU.REPOSITORY/24901http://dx.doi.org/10.1039/c0pp00372g
ISSN
1474-905X
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이과대학 > 화학생화학부 > Articles
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