Fullerene C<sub>60</sub> promoted photochemical hydroamination reactions of an electron deficient alkyne with trimethylsilyl group containing tertiary <i>N</i>-alkylbenzylamines

Lim, Suk Hyun; Jang, Hannara; Cho, Dae-Won

doi:10.1039/d1ra00166c

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“…Inspired by the above results and our recent study on the single electron transfer (SET)-promoted photoaddition reaction of α-silylamines, , we envisioned that visible light-induced photooxygenation reactions of highly electron-deficient enaminoesters using a metal-free organic photosensitizer, which can serve as an efficient 1 O 2 -generating photosensitizer, might generate dioxetane intermediates, which would undergo a cycloreversion process to form oxamate analogues. To verify this synthetic protocol, we prepared several types of di(carboxymethyl) group-containing enaminoesters and carried out photochemical reactions of them in the presence of methylene blue (MB).…”

Section: Introductionmentioning

confidence: 99%

Silyl Tether-Assisted Photooxygenation of Electron-Deficient Enaminoesters: Direct Access to Oxamate Formation

et al. 2022

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Photooxygenation reactions of electron-deficient enaminoesters bearing an oxophilic silyl tether at the α-position of the nitrogen atom using methylene blue (MB) were explored to develop a mild and efficient photochemical strategy for oxidative C−C double bond cleavage reactions via singlet oxygen ( 1 O 2 ). Photochemically generated 1 O 2 , through energy transfer from the triplet excited state of MB ( 3 MB*) to molecular oxygen ( 3 O 2 ), was added across a C−C double bond moiety of enaminoesters to form perepoxides, which rearranged to form dioxetane intermediates. The cycloreversion of the formed dioxetane via both C−C and O−O bond cleavage processes led to the formation of oxamates. Importantly, contrary to alkyl group tether-substituted electrondeficient enaminoesters that typically disfavor photooxygenation, the silyl tether-substituted analogues undergo this photochemical transformation efficiently with the assistance of a silyl tether, which facilitates formation of the perepoxide. The observations in this study provide useful information about photosensitized oxygenation 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 including oxamates.

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Section: Introductionmentioning

confidence: 99%

Silyl Tether-Assisted Photooxygenation of Electron-Deficient Enaminoesters: Direct Access to Oxamate Formation

et al. 2022

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Fullerene C₆₀ promoted photochemical hydroamination reactions of an electron deficient alkyne with trimethylsilyl group containing tertiary N-alkylbenzylamines

Abstract: C60-promoted photoaddition reactions of N-α-trimethylsilyl-N-alkylbenzylamines with dimethyl acetylenedicarboxylate (DMAD) were carried out.

Cited by 1 publication

References 45 publications

Silyl Tether-Assisted Photooxygenation of Electron-Deficient Enaminoesters: Direct Access to Oxamate Formation

Silyl Tether-Assisted Photooxygenation of Electron-Deficient Enaminoesters: Direct Access to Oxamate Formation

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Fullerene C60 promoted photochemical hydroamination reactions of an electron deficient alkyne with trimethylsilyl group containing tertiary N-alkylbenzylamines

Abstract: C60-promoted photoaddition reactions of N-α-trimethylsilyl-N-alkylbenzylamines with dimethyl acetylenedicarboxylate (DMAD) were carried out.

Cited by 1 publication

References 45 publications

Silyl Tether-Assisted Photooxygenation of Electron-Deficient Enaminoesters: Direct Access to Oxamate Formation

Silyl Tether-Assisted Photooxygenation of Electron-Deficient Enaminoesters: Direct Access to Oxamate Formation

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Fullerene C₆₀ promoted photochemical hydroamination reactions of an electron deficient alkyne with trimethylsilyl group containing tertiary N-alkylbenzylamines