"Front Matter". In: Organosilanes in Radical Chemistry - Index of
"Front Matter". In: Organosilanes in Radical Chemistry - Index of "Front Matter". In: Organosilanes in Radical Chemistry - Index of
References 47 16. Rong, X.X., Pan, H.-Q., Dolbier, Jr., W.R., and Smart, B.E., J. Am. Chem. Soc., 1994, 116, 4521. 17. Shtarev, A.B., Dolbier, Jr., W.R., and Smart, B.E., J. Am. Chem. Soc., 1999, 121, 2110. 18. Dolbier, Jr., W.R., and Li, A.-R., J. Chem. Soc., Perkin Trans. 2, 1998, 79. 19. Baruch, G., and Horowitz, A., J. Phys. Chem., 1980, 84, 2535. 20. Chatgilialoglu, C., Ferreri, C., Lucarini, M., Venturini, A., and Zavitsas A.A., Chem. Eur. J., 1997, 3, 376. 21. Lucarini, M., Marchesi, E., Pedulli, G.F., and Chatgilialoglu, C., J. Org. Chem., 1998, 63, 1687. 22. Varlamov, V.T., Denisov, E.T., and Chatgilialoglu, C., J. Org. Chem., 2001, 66, 6317. 23. Chatgilialoglu, C., Scaiano, J.C ., and Ingold, K.U., Organometallics, 1982, 1, 466. 24. Chatgilialoglu, C., Ingold, K.U., Lusztyk, J., Nazran, A.S., and Scaiano, J.C., Organometallics, 1983, 2, 1332. 25. Lusztyk, J., Maillard, B., and Ingold, K.U., J. Org. Chem., 1986, 51, 2457. 26. Chatgilialoglu, C., and Rossini, S., Bull. Soc. Chim. Fr., 1988, 298. 27. Chatgilialoglu, C., Guerra, M., Guerrini, A., Seconi, G., Clark, K.B., Griller, D., Kanabus-Kaminska, J., and Martinho-Simões, J.A., J. Org. Chem., 1992, 57, 2427. 28. Lee, Y.E., and Choo, K.Y., Int. J. Chem. Kinet., 1986, 18, 267. 29. Chatgilialoglu, C., Timokhin, V.I., Zaborovskiy, A.B., Lutsyk, D.S., and Prystansky, R.E., J. Chem. Soc., Perkin Trans. 2, 2000, 577. 30. Chatgilialoglu, C., Malatesta, V., and Ingold, K.U., J. Phys. Chem., 1980, 84, 3597. 31. Doba, T., and Ingold, K.U., J. Am. Chem. Soc., 1984, 106, 3958. 32. Chateauneuf, J., Lusztyk, J., and Ingold, K.U., J. Am. Chem. Soc., 1988, 110, 2886. 33. Roberts, B.P., Chem. Soc. Rev., 1999, 28, 25. 34. Cai, Y., and Roberts, B.P., J. Chem. Soc., Perkin Trans. 2, 2002, 1858. 35. Müller, U., Helmstreit, W., and Timpe, H.-J., J. Photochem Photobiol. A: chem., 1989, 50, 1. 36. Arthur, N.L., and Miles, L.A., J. Chem. Soc., Faraday Trans., 1998, 94, 1077. 37. Yu, X., Li, S.-M., Xu, Z.-F., Li, Z.-S., and Sun, C.-C., J. Phys. Chem. A, 2001, 105, 7072. 38. Arthur, N.L., Potzinger, P., Reimann, B., and Steenbergen, H-P., J. Chem. Soc., Faraday Trans., 1989, 85, 1447. 39. Dakternieks, D., Henry, D.J., and Schiesser, C.H. J. Chem. Soc., Perkin Trans. 2, 1998, 591. 40. Zavitsas, A.A., and Chatgilialoglu, C., J. Am. Chem. Soc., 1995, 117, 10645. 41. Zavitsas, A.A., J. Am. Chem. Soc., 1998, 120, 6578. 42. Roberts, B.P., and Steel, A.J., J. Chem. Soc., Perkin Trans. 2, 1994, 2155. 43. Denisov, E.T., Russ. Chem. Bull., 1998, 47, 1274.
4 Reducing Agents 4.1 GENERAL ASPECTS OF RADICAL CHAIN REACTIONS The use of free-radical reactions in organic synthesis started with the reduction of functional groups. The purpose of this chapter is to give an overview of the relevance of silanes as efficient and effective sources for facile hydrogen atom transfer by radical chain processes. A number of reviews [1–7] have described some specific areas in detail. Reaction (4.1) represents the reduction of a functional group by silicon hydride which, in order to be a radical chain process, has to be associated with initiation, propagation and termination steps of the radical species. Scheme 4.1 illustrates the insertion of Reaction (4.1) in a radical chain process. RZ þ R 0 3SiH !RH þ R0 3SiZ (4:1) A large number of compounds are known to decompose thermally or photolytically to generate free radicals (see Section 4.2). These radicals (In:) participate in the initiation step by abstracting a hydrogen atom from the reducing SiH. In the propagation steps, the removal of the functional group Z in agent R0 3 the organic substrate takes place by action of R0 3Si: radical via a reactive intermediate or a transition state represented by [RZ(:)SiR0 3 ]. A site-specific radical R: is generated, which then reacts with the silicon hydride and gives the reduced product, together with ‘fresh’ R0 3Si: radicals to continue the chain. Chain reactions terminate by radical–radical combination or disproportionation reactions, with the general concept that the more remote the termination reactions the more efficient is the chain reaction. Kinetically speaking, to be efficient the rate of chain transfer steps between radicals and starting materials must be higher than that of chain termination steps between radicals. The Organosilanes in Radical Chemistry C. Chatgilialoglu # 2004 John Wiley & Sons, Ltd ISBN: 0-471-49870-X
- Page 3 and 4: DEDICATION To my parents XrZstoB an
- Page 5 and 6: viii Contents 3.6 Hydrogen Atom: An
- Page 7 and 8: PREFACE A large number of papers de
- Page 9 and 10: ACKNOWLEDGEMENTS I thank Keith U. I
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- Page 31 and 32: Bond Dissociation Enthalpies 23 2.2
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- Page 77 and 78: Other Silicon Hydrides 71 The reduc
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References 47<br />
16. Rong, X.X., Pan, H.-Q., Dolbier, Jr., W.R., and Smart, B.E., J. Am. Chem. Soc.,<br />
1994, 116, 4521.<br />
17. Shtarev, A.B., Dolbier, Jr., W.R., and Smart, B.E., J. Am. Chem. Soc., 1999, 121,<br />
2110.<br />
18. Dolbier, Jr., W.R., and Li, A.-R., J. Chem. Soc., Perk<strong>in</strong> Trans. 2, 1998, 79.<br />
19. Baruch, G., and Horowitz, A., J. Phys. Chem., 1980, 84, 2535.<br />
20. Chatgilialoglu, C., Ferreri, C., Lucar<strong>in</strong>i, M., Ventur<strong>in</strong>i, A., and Zavitsas A.A.,<br />
Chem. Eur. J., 1997, 3, 376.<br />
21. Lucar<strong>in</strong>i, M., Marchesi, E., Pedulli, G.F., and Chatgilialoglu, C., J. Org. Chem.,<br />
1998, 63, 1687.<br />
22. Varlamov, V.T., Denisov, E.T., and Chatgilialoglu, C., J. Org. Chem., 2001, 66,<br />
6317.<br />
23. Chatgilialoglu, C., Scaiano, J.C ., and <strong>In</strong>gold, K.U., Organometallics, 1982, 1, 466.<br />
24. Chatgilialoglu, C., <strong>In</strong>gold, K.U., Lusztyk, J., Nazran, A.S., and Scaiano, J.C.,<br />
Organometallics, 1983, 2, 1332.<br />
25. Lusztyk, J., Maillard, B., and <strong>In</strong>gold, K.U., J. Org. Chem., 1986, 51, 2457.<br />
26. Chatgilialoglu, C., and Ross<strong>in</strong>i, S., Bull. Soc. Chim. Fr., 1988, 298.<br />
27. Chatgilialoglu, C., Guerra, M., Guerr<strong>in</strong>i, A., Seconi, G., Clark, K.B., Griller, D.,<br />
Kanabus-Kam<strong>in</strong>ska, J., and Mart<strong>in</strong>ho-Simões, J.A., J. Org. Chem., 1992, 57, 2427.<br />
28. Lee, Y.E., and Choo, K.Y., <strong>In</strong>t. J. Chem. K<strong>in</strong>et., 1986, 18, 267.<br />
29. Chatgilialoglu, C., Timokh<strong>in</strong>, V.I., Zaborovskiy, A.B., Lutsyk, D.S., and Prystansky,<br />
R.E., J. Chem. Soc., Perk<strong>in</strong> Trans. 2, 2000, 577.<br />
30. Chatgilialoglu, C., Malatesta, V., and <strong>In</strong>gold, K.U., J. Phys. Chem., 1980, 84, 3597.<br />
31. Doba, T., and <strong>In</strong>gold, K.U., J. Am. Chem. Soc., 1984, 106, 3958.<br />
32. Chateauneuf, J., Lusztyk, J., and <strong>In</strong>gold, K.U., J. Am. Chem. Soc., 1988, 110, 2886.<br />
33. Roberts, B.P., Chem. Soc. Rev., 1999, 28, 25.<br />
34. Cai, Y., and Roberts, B.P., J. Chem. Soc., Perk<strong>in</strong> Trans. 2, 2002, 1858.<br />
35. Müller, U., Helmstreit, W., and Timpe, H.-J., J. Photochem Photobiol. A: chem.,<br />
1989, 50, 1.<br />
36. Arthur, N.L., and Miles, L.A., J. Chem. Soc., Faraday Trans., 1998, 94, 1077.<br />
37. Yu, X., Li, S.-M., Xu, Z.-F., Li, Z.-S., and Sun, C.-C., J. Phys. Chem. A, 2001, 105,<br />
7072.<br />
38. Arthur, N.L., Potz<strong>in</strong>ger, P., Reimann, B., and Steenbergen, H-P., J. Chem. Soc.,<br />
Faraday Trans., 1989, 85, 1447.<br />
39. Dakternieks, D., Henry, D.J., and Schiesser, C.H. J. Chem. Soc., Perk<strong>in</strong> Trans. 2,<br />
1998, 591.<br />
40. Zavitsas, A.A., and Chatgilialoglu, C., J. Am. Chem. Soc., 1995, 117, 10645.<br />
41. Zavitsas, A.A., J. Am. Chem. Soc., 1998, 120, 6578.<br />
42. Roberts, B.P., and Steel, A.J., J. Chem. Soc., Perk<strong>in</strong> Trans. 2, 1994, 2155.<br />
43. Denisov, E.T., Russ. Chem. Bull., 1998, 47, 1274.
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