Journal of Photoscience

한국광과학회 (Korean Society of Photoscience)
권호 표지

Photoaddition Reactions of N-Methylthiophthalimide with $\alpha$-Silyl-n-electron Donors via Single Electron Transfer-Desilylation and Hydrogen Atom Abstraction Pathways

  • Yoon, Ung-Chan (Department of Chemistry and Chemistry Institute for Functional Materials) ;
  • Oh, Sun-Wha (Department of Chemistry and Chemistry Institute for Functional Materials) ;
  • Moon, Seong-Chul (Department of Chemistry and Chemistry Institute for Functional Materials) ;
  • Hyung, Tae-Gyung (Department of Chemistry and Chemistry Institute for Functional Materials)
  • 발행 : 2002.03.01
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초록

Studies have been conducted to explore photoaddition reactions of N-methylthiophthalimide with $\alpha$-silyl-n-electron donors Et$_2$NCH$_2$SiMe$_3$, n-PrSCH$_2$SiMe$_3$ and EtOCH$_2$SiMe$_3$. Photoaddition of $\alpha$-silyl amine Et$_2$NCH$_2$SiMe$_3$ to N-methylthiophthalimide occurs in $CH_3$CN and benzene to produce non-silicon containing adduct in which thiophthalimide thione carbon is bonded to $\alpha$-carbon of $\alpha$-silyl amine in place of the trimethylsilyl group. In contrast, photoaddition of EtOCH$_2$SiMe$_3$ to N-methylthiophthalimide generates two diastereomeric adducts in which thiophthalimide thione carbon is connected to $\alpha$-carbon of $\alpha$-silyl ether in place of u-hydrogen. Based on a consideration of the oxidation potentials of u-silyl-n-electron donors and the nature of photoadducts, mechanism for these photoadditions involving single electron transfer(SET) -desilylation and H atom abstraction pathways are proposed.

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참고문헌

  1. Acc. Chem. Res. v.11 Photoreactions of Cyclic Imides. Examples of Synthetic Organic Photochemistry Kanaoka, Y.
  2. Synthetic Organic Photochemistry Phthalimide and Its Derivatives. Colye, J. D.;Horsepool, W. M.(ed.)
  3. Organic Photochemistry v.5 The Photochemistry of Imides Mazzocchi, P. H.;Padwa, A.(ed.)
  4. J. Am. Chem. Soc. v.119 Photochemical Mechanisms Responsible for the Versatile Application of Napthalimides and Naphthaldiimides in Biological Systems Aveline, B. M.;Matsuga, S.;Redmond, R. W.
  5. J. Am. Chem. Soc. v.119 no.22 The Dynamics of α-Anilino Carboxylate and Related Cation Radical α-Heterolytic Fragmentations Su, Z.;Falvey, D. E.;Yoon, U. C.;Mariano, P. S.
  6. J. Am. Chem. Soc. v.120 no.41 Dynamics of Anilinium Radical α-Heterolytic Fragmentation Processes. Electrofugal Group, Substituent, and Medium Effects on Desilylation, Decarboxylation, and Retro-Aldol Cleavage Pathways Su, Z.;Mariano, P.S.;Falvey, D. E.;Yoon, U. C.;Oh, S. W.
  7. Electrochemical and Theoretical Studies v.112 The Origin of β-Silicon Effect in Electron-Transfer Reactions of Silicon-Substituted Heteroatom Compound Yoshida, J.;Maekawa, T.;Murata, T.;Matsunaga, S.;Isoe, S.
  8. Tetrahedron Lett. v.28 no.52 Electrochemical oxidation of α-silylcarbamates 1 Yoshida, J.;Isoe, S.
  9. J. Organomet. Chem. v.29 no.1 Silicon-carbon hyperconjugation in cation radicals Ⅰ. Lowering of oxidation potentials of N-[(trimethylsilyl)methyl]aromatic amines Cooper, B. E.;Owen, W. J.
  10. J. Am. Chem. Soc. v.104 A Novel Method for Heteroatom-Substituted Free Radical Generation by Photochemical Electron-Transfer-Induced Desilylation of $RXCH_2SiMe_3$ Systems Brumfield, M. A.;Quillen, S. L.;Yoon, U. C.;Mariano, P. S.
  11. J. Org. Chem. v.49 no.2 Exploratory and Mechanistic Studies of the Electron-Transfer-Initiated Photoaddition Reactions of Allylsilane-Iminium Salt System Ohga, K.;Yoon, U. C.;Mariano, P.S.
  12. J. Org. Chem. v.53 no.23 Photoadditions of Ethers, Thioethers, and Amines to 9,10-Dicyanoanthracene by Electron Transfer Pathways Hasegawa, E.;Brumfield, M. A.;Mariano, P. S.;Yoon, U. C.
  13. J. Am. Chem. Soc. v.109 Electron-Transfer Photochemistry of α-Silylamine-Cyclohexenone Systems. Medium Effects on Reaction Pathways Followed Yoon, U. C.;Kim, J. U.;Hasegawa, E.;Mariano, P. S.
  14. J. Am. Chem. Soc. v.110 Electron Transfer-Induced Photoadditions of the Silylamine, $Et_2NCH_2TMS$ to α,β-unsaturated Cyclohexenones. Dual Reaction Pathways Based on Ion-Pair-Selective Cation Radical Chemistry Hasegawa, E.;Xu, W.;Mariano, P. S.;Yoon, U. C.;Kim, J. U.
  15. J. Org. Chem. v.57 Photoaddition Reactions of Acenaphthylenedione with α-Silyl-n-Electron Donors via Triplet Single Electron Transfer-Desilylation and Triplet Hydrogen Atom Abstraction Pathways Yoon, U. C.;Kim, Y. C.;Choi, J. J.;Kim, D. U.;Mariano, P.S.;Cho, I. S.;Jeon, Y. T.
  16. Acc. Chem. Res. v.25 Mechanistic and Synthetic Aspects of Amine-Enone Single Electron Transfer Photochemistry Yoon, U. C.;Mariano, P. S.
  17. Advances in Electron Transfer Chemistry v.4 Photoinduced Electron Transfer Chemistry of Amine and Related Electron Donors Yoon, U. C.;Mariano, P. S.;Givens, R. S.;Atwater, B. W.;Mariano, P. S.(ed.)
  18. Heterocycles v.29 Electron Transfer Induced Photochemical Reactions in Imide Systems. Photoaddition of α-Trimethtlsilylmethyl Substituted Heteroatom Containing Compounds to Phthalimides Yoon, U. C.;Kim, H. J.;Mariano, P. S.
  19. Bull. Korean Chem. Soc. v.13 no.2 Photocyclization Reactions of N-(Trimethylsilylmethoxy)phthalimides. Efficient and Regioselective Route to Heterocycles Yoon, U. C.;Oh, J. H.;Lee, S. J.;Kim, D. U.;Lee, J. G.;Kang, K. T.;Mariano, P. S.
  20. Bull. Korean Chem. Soc. v.15 no.2 Exploratory Studies of Photocyclization Reactions of N-(Trimethylsilylmethylthio alkyl)phthalimides Yoon, U. C.;Lee, S. J.;Lee, K. J.;Lee, C. W.;Cho, S. J.;Mariano, P. S.
  21. J. Photochem. Photobiol. A Single Electron Transfer Induced Photocyclization Reactions of N-[(N-Trimethylsilylmethyl) aminoalkyl]phthalimides Yoon, U. C.;Kim, J. W.;Ryu, J. Y.;Cho, S. J.;Oh, S. W.;Mariano, P. S.
  22. Heterocycles v.41 Efficient and Regiioselective Photocyclization Reactions of N-[(ω-Trimethylsilylmethylmethoxy)polyoxaalkyl] phthalimides to Azocrown Ethers Yoon, U. C.;Oh, S. W.;Lee, C. W.
  23. J. Org. Chem. v.66 Applications of Phthalimide Photochemistry to Macrocyclic Polyether, Polythioether and Polyamide Synthesis Yoon, U. C.;Oh, S. W.;Lee, J. H.;Park, J. H.;Kang, K. T.;Mariano, P. S.
  24. Heterocycles v.23 Photocycloaddition of N-Methylmonothiophthalimide with Styrene Derivatives Accompanied by 1,2-Dithiane Formation Machida, M.;Oda, K.;Yoshida, E.;Wakao, S.;Ohno, K.
  25. J. Chem. Soc. Perkin Trans.Ⅰ Photochemical Cycloaddition Reactions of N-Methyl(thiophthalimide) and N-Methyl(dithiophthalimide) with Alkenes Coyle, J. D.;Rapley, P. A.
  26. J. Chem. Soc. Perkin Trans.Ⅰ Photocycloaddition Reactions of Thioimides with Alkynes Coyle, J. D.;Rapley, P. A.
  27. J. Photochem. v.31 Photocyclization Reactions of N-Substituted Thiophthalimides Coyle, J.D.;Rapley, P.A.
  28. J. Chem. Soc. Perkin Trans. Ⅰ Photochemical Cycloaddition of Thiocarbonyl Compounds to Diphenylketene and a Related Ketenimine Coyle, J. D.;Rapley, P. A.
  29. Chem. Pharm. Bull. v.37 The Norrish Type Ⅱ Reaction of Thiophthalimides Having a Benzylic Hydrogen in an N-Alkyl Side Chain Oda, K.;Yoshida, E.;Ohno, K.;Machida, M.;Kanaoka, Y.
  30. J. Org. Chem. v.50 Photochemistry of the Thioimide Systems : Imide-Thietanes Machida, M.;Oda, K.;Yoshida, E.;Kanaoka, Y.
  31. Tetrahedron Lett. v.26 The Norrish Type Ⅱ Reaction of the Cyclic Thioimides with a Benzylic Hydrogen Machida, M.;Oda, K.;Kanaoka, Y.
  32. Chem. Pharm. Bull. v.34 Intramolecular Photocyclization of 3-Substituted Alicyclic Dithioimides : Facile Synthesis of 2-Azabicycloalkanes via the Norrish Type Ⅱ process Machida, M.;Oda, K.;Kanaoka, Y.
  33. Synthesis Intramolecular Photocycloaddition of Ring-Substituted Cyclic Dithoimides with 2,3-Dimethyl-2-butene : A Facile Synthesis of Spiro-Thiethanes Oda, K.;Machida, M.;Kanaoka, Y.
  34. Norrish type Ⅱ reactions of thioimides have been reported [12f, 13e]
  35. The formation of N-methylphthalimide (1) in the photoreaction of N-methylthiophthalimide (5) in the presence of O₂has been reported [12d] and inefficient generation of 1 in the photoreaction of 5 with α-silyl thioether 3 is believed to arise from the photoreaction of 5 with O₂impurity present in the reaction solution under Ar purging