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130th General Meeting of Korean Chemical Society Photooxygenation of Oxophilic Silyl Group Containing Electron-Deficient Enaminoesters: Direct Access to Oxamates Formation

Submission Date :
8 / 3 / 2022 , 17 : 53 : 18
Abstract Number :
Presenting Type:
Poster Presentation
Presenting Area :
Organic Chemistry
Authors :
Suk hyun Lim, Hye Mi Yoo, Dae won Cho*
Department of Chemistry, Yeungnam University, Korea
Assigned Code :
Presenting Time :
Photooxygenation reactions of oxophilic silyl group containing, electron-deficient enaminoesters using methylene blue (MB) were explored to develop a mild and efficient photochemical strategy for the oxidative C-C double bond cleavage reactions via singlet oxygen (1O2). The photochemically generated 1O2, through energy transfer from triplet excited state of MB (3MB*) to molecular oxygen (3O2), was added across a C-C double bond moiety of enaminoesters to form perperoxide, which rearranged to form dioxetane intermediates. The cycloreversion of formed dioxetanes via both C-C and O-O bond cleavage processes led to the formation of oxamates. Importantly, contrary to non-silyl group containing, electron-deficient enaminoester analogs that typically disfavor photooxygenation, the silyl group, positioned at the alpha-position of nitrogen within electron-deficient enaminoesters atom, played an essential role in the success of this photochemical transformation. The observation of this study provides useful information about the Photooxygenation reactions of unsaturated C-C bonds and, moreover, this photochemical strategy can be utilized as a mild and feasible method for the preparation of diversely functionalized carbonyl compounds.