Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

다국어 초록 (Multilingual Abstract)

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior.
Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature . Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and γ-hydrogen abstraction pathways.

참고문헌 (Reference)

1 Yoon, U. C., 34 (34): 523-, 2001

2 Yoon, U. C., 125 : 10664-, 2003

3 Cooper, B. E., 29 : 33-, 1971

4 Yoon, U. C., 15 (15): 743-, 1994

5 Yoon, U. C., 41 (41): 2665-, 1995

6 Yoon, U. C., 126 : 1110-, 2004

7 Cho, D. W., 73 (73): 4539-, 2008

8 Kanaoka, Y., 4517-, 1972

9 Coyle, J. D., 78 : 97-, 1978

10 Kanaoka, Y., 44 : 664-, 1979

11 Kanaoka, Y., 11 : 407-, 1978

12 Kanaoka, Y., 96 : 4719-, 1974

13 Coyle, J. D., 799-, 1979

14 Oelgemoller, M., 3 : 109-, 2002

15 Dinnocenzo, J. P., 111 : 8973-, 1989

16 Yoon, U. C., 64 : 4411-, 1999

17 Sung, N. K., 72 : 8831-, 2007

18 Cho, D. W., 130 (130): 2276-, 2008

19 Cho, D. W., 66 : 3173-, 2010

20 Maeda, H., 64 (64): 5268-, 2008

21 Yoon, U. C., 13 (13): 166-, 1992

22 Yoon, U. C., 177 : 2698-, 1995

23 Yoon, U. C., 60 : 2353-, 1995

24 Lee, Y. J., 61 : 3304-, 1996

25 Yoon, U. C., 106 : 145-, 1997

26 Yoon, U. C., 55 : 11997-, 1999

27 Kamigata, N., 1 : 9-, 1997

28 Ono, I., 70 : 2051-, 1997

29 Ung Chan Yoon*, "The Synthetic Potential of SET Photochemistry of Silicon-Substituted Polydonor-Linked Phthalimides" 대한화학회 27 (27): 1099-1114, 2006

30 Sun Wha Oh, "Single Electron Transfer Induced Photoaddition Reactions of Silyl Enol Ether to N-Methylphthalimide" 대한화학회 28 (28): 629-634, 2007

31 Cowan, D. O., "Elements of Organic Photochemistry. Chapter 5" Plenum Press 205-266, 1976