Lifetimes of dialkylcarbocations derived from alkanediazonium ions in solution: Cyclohexadienyl cations as kinetic probes for cation reactivity

Journal of the American Chemical Society

Volumn 121, Issue 28, 1999, Pages 6589-6598

  Pezacki, John Paul ^a,b,c   Shukla, Deepak ^b   Lusztyk, Janusz ^b   Warkentin, John ^a  

^a MCMASTER UNIVERSITY   (Canada)

^b NATIONAL RESEARCH COUNCIL CANADA   (Canada)

^c UNIVERSITY OF TORONTO   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; CATION; DIAZONIUM COMPOUND;

ALKYLATION; ARTICLE; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; CHEMOREACTIVITY; MOLECULAR PROBE; PHOTOLYSIS; REACTION ANALYSIS;

EID: 0033591912     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9840807     Document Type: Article

References (135)

1. Issued as NRCC No. 42179.
2. Griess, P. Justus Liebigs Ann. Chem. 1861, 120, 125.
3. Lijinsky, W. In Chemistry and Biology of N-nitroso Compounds; Cambridge University Press: Cambridge, 1992.
4. (a) Druckrey, H.; Preussmann, R.; Ivankovic, S.; Schmahl, D. Z. Krebsforsch. 1967, 69, 103.
5. (b) Druckrey, H. Xenobiotica 1973, 3, 271.
6. Lijinsky, W. IARC Sci. Publ. 1982, 41, 533.
7. (a) Mesić, M.; Revis, C.; Fishbein, J. C. J. Am. Chem. Soc. 1996, 118, 7412.
8. (b) Chahoua, L.; Mesić, M.; Revis, C.; Vigroux, A.; Fishbein, J. C. J. Org. Chem. 1997, 62, 2500.
9. (a) Ukawa, S.; Tobita, C.; Mochizuki, M. Mutat. Res. 1988, 203, 391.
10. (b) Ukawa, S.; Mochizuki, M. Mutat. Res. 1991, 252, 391.
11. (a) Moss, R. A. Acc. Chem. Res. 1974, 7, 421.
12. (b) Moss, R. A.; Powell, C. E. J. Am. Chem. Soc. 1976, 98, 284.
13. (c) White, E. H.; Field, K. W. J. Am. Chem. Soc. 1975, 97, 2148.
14. (a) Finneman, J. I.; Fishbein, J. C. J. Am. Chem. Soc. 1996, 118, 7134.
15. (b) Finneman, J. I.; Fishbein, J. C. J. Am. Chem. Soc. 1995, 117, 4228.
16. (c) Ho, J.; Fishbein, J. C. J. Am. Chem. Soc. 1994, 116, 6611.
17. (d) Finneman, J. I.; Ho, J.; Fishbein, J. C. J. Am. Chem. Soc. 1993, 115, 3016.
18. (e) Hovinen, J.; Finneman, J. I.; Satapathy, S. N.; Ho, J.; Fishbein, J. C. J. Am. Chem. Soc. 1992, 114, 10321.
19. (f) Gold, B.; Deshpande, A.; Linder, W.; Hines, L. J. Am. Chem. Soc. 1984, 106, 2072.
20. For reviews of aliphatic diazonium ion chemistry, see: (a) Laali, K.; Olah, G. A. Rev. Chem. Intermed. 1986, 6, 237. (b) Kirmse, W. Angew. Chem., Int. Ed. Engl. 1976, 15, 251. (c) Collins, C. J. Acc. Chem. Res. 1971, 4, 315. (d) More O'Ferrall, R. A. Adv. Phys. Org. Chem. 1967, 5, 331. (e) Huisgen, R. Angew. Chem. 1955, 67, 273. (f) Zollinger, H. In Diazo Chemistry; VCH Publ.: New York, 1995; Vol. 1-2. (g) Whittaker, D. In The Chemistry of Diazonium and Diazo Compounds; Patai, S., Ed.; Wiley- Interscience: Chichester, 1978; pp 617-639.
21. For reviews of aliphatic diazonium ion chemistry, see: (a) Laali, K.; Olah, G. A. Rev. Chem. Intermed. 1986, 6, 237. (b) Kirmse, W. Angew. Chem., Int. Ed. Engl. 1976, 15, 251. (c) Collins, C. J. Acc. Chem. Res. 1971, 4, 315. (d) More O'Ferrall, R. A. Adv. Phys. Org. Chem. 1967, 5, 331. (e) Huisgen, R. Angew. Chem. 1955, 67, 273. (f) Zollinger, H. In Diazo Chemistry; VCH Publ.: New York, 1995; Vol. 1-2. (g) Whittaker, D. In The Chemistry of Diazonium and Diazo Compounds; Patai, S., Ed.; Wiley- Interscience: Chichester, 1978; pp 617-639.
22. For reviews of aliphatic diazonium ion chemistry, see: (a) Laali, K.; Olah, G. A. Rev. Chem. Intermed. 1986, 6, 237. (b) Kirmse, W. Angew. Chem., Int. Ed. Engl. 1976, 15, 251. (c) Collins, C. J. Acc. Chem. Res. 1971, 4, 315. (d) More O'Ferrall, R. A. Adv. Phys. Org. Chem. 1967, 5, 331. (e) Huisgen, R. Angew. Chem. 1955, 67, 273. (f) Zollinger, H. In Diazo Chemistry; VCH Publ.: New York, 1995; Vol. 1-2. (g) Whittaker, D. In The Chemistry of Diazonium and Diazo Compounds; Patai, S., Ed.; Wiley- Interscience: Chichester, 1978; pp 617-639.
23. For reviews of aliphatic diazonium ion chemistry, see: (a) Laali, K.; Olah, G. A. Rev. Chem. Intermed. 1986, 6, 237. (b) Kirmse, W. Angew. Chem., Int. Ed. Engl. 1976, 15, 251. (c) Collins, C. J. Acc. Chem. Res. 1971, 4, 315. (d) More O'Ferrall, R. A. Adv. Phys. Org. Chem. 1967, 5, 331. (e) Huisgen, R. Angew. Chem. 1955, 67, 273. (f) Zollinger, H. In Diazo Chemistry; VCH Publ.: New York, 1995; Vol. 1-2. (g) Whittaker, D. In The Chemistry of Diazonium and Diazo Compounds; Patai, S., Ed.; Wiley- Interscience: Chichester, 1978; pp 617-639.
24. For reviews of aliphatic diazonium ion chemistry, see: (a) Laali, K.; Olah, G. A. Rev. Chem. Intermed. 1986, 6, 237. (b) Kirmse, W. Angew. Chem., Int. Ed. Engl. 1976, 15, 251. (c) Collins, C. J. Acc. Chem. Res. 1971, 4, 315. (d) More O'Ferrall, R. A. Adv. Phys. Org. Chem. 1967, 5, 331. (e) Huisgen, R. Angew. Chem. 1955, 67, 273. (f) Zollinger, H. In Diazo Chemistry; VCH Publ.: New York, 1995; Vol. 1-2. (g) Whittaker, D. In The Chemistry of Diazonium and Diazo Compounds; Patai, S., Ed.; Wiley- Interscience: Chichester, 1978; pp 617-639.
25. For reviews of aliphatic diazonium ion chemistry, see: (a) Laali, K.; Olah, G. A. Rev. Chem. Intermed. 1986, 6, 237. (b) Kirmse, W. Angew. Chem., Int. Ed. Engl. 1976, 15, 251. (c) Collins, C. J. Acc. Chem. Res. 1971, 4, 315. (d) More O'Ferrall, R. A. Adv. Phys. Org. Chem. 1967, 5, 331. (e) Huisgen, R. Angew. Chem. 1955, 67, 273. (f) Zollinger, H. In Diazo Chemistry; VCH Publ.: New York, 1995; Vol. 1-2. (g) Whittaker, D. In The Chemistry of Diazonium and Diazo Compounds; Patai, S., Ed.; Wiley- Interscience: Chichester, 1978; pp 617-639.
26. For reviews of aliphatic diazonium ion chemistry, see: (a) Laali, K.; Olah, G. A. Rev. Chem. Intermed. 1986, 6, 237. (b) Kirmse, W. Angew. Chem., Int. Ed. Engl. 1976, 15, 251. (c) Collins, C. J. Acc. Chem. Res. 1971, 4, 315. (d) More O'Ferrall, R. A. Adv. Phys. Org. Chem. 1967, 5, 331. (e) Huisgen, R. Angew. Chem. 1955, 67, 273. (f) Zollinger, H. In Diazo Chemistry; VCH Publ.: New York, 1995; Vol. 1-2. (g) Whittaker, D. In The Chemistry of Diazonium and Diazo Compounds; Patai, S., Ed.; Wiley-Interscience: Chichester, 1978; pp 617-639.
27. McGarrity, J. F.; Smyth, T. J. Am. Chem. Soc. 1980, 102, 7303.
28. (a) Berner, D.; McGarrity, J. F. J. Am. Chem. Soc. 1979, 101, 3135.
29. (b) McGarrity, J. F.; Cox, D. P. J. Am. Chem. Soc. 1983, 105, 3961.
30. Brosch, D.; Kirmse, W. J. Org. Chem. 1991, 56, 907 and refs therein.
31. Glaser, R.; Choy, G. S.-C.; Hall, M. K. J. Am. Chem. Soc. 1991, 113, 1109.
32. Glaser, R.; Choy, G. S.-C. J. Am. Chem. Soc. 1993, 115, 2340.
33. Kirmse, W.; Schnurr, O.; Jendralla, H. Chem. Ber. 1979, 112, 2120.
34. Southam, R. M.; Whiting, M. C. J. Chem. Soc., Perkin Trans. 2 1982, 1228.
35. For examples of such arguments, see: ref 8a and references therein.
36. Mohrig, J. R.; Keegstra, K.; Maverick, A.; Roberts, R.; Wells, S. J. Chem. Soc., Chem. Commun. 1974, 780.
37. Berner, D.; McGarrity, J. F. J. Am. Chem. Soc. 1979, 101, 3135.
38. Bunse, M.; Kirmse, W. Chem. Ber. 1993, 126, 1499.
39. McClelland, R. A. Tetrahedron 1996, 52, 6823 and references therein.
40. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
41. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
42. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
43. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
44. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
45. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
46. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
47. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
48. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
49. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
50. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
51. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
52. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
53. For examples, see: (a) Hagen, G.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 4954. (b) Irrgang, B.; Mayr, H. Tetrahedron Lett. 1991, 47, 219. (c) Mayr, H.; Schnieder, R.; Grabis, U.. J. Am. Chem. Soc. 1990, 112, 4460. (d) Mayr, H.; Schnieder, R.; Irrgang, B.; Schade, C J. Am. Chem. Soc. 1990, 112, 4454. (e) Mayr, H.; Schnieder, R.; Schade, C; Bartl, J.; Bederke, R. J. Am. Chem. Soc. 1990, 112, 4446. (f) Mayr, H. Angew. Chem., Int. Ed. Engl. 1990, 29, 1371. (g) Bartl, J.; Steenken, S.; Mayr, H. J. Am. Chem. Soc. 1991, 113, 7710. (h) Roth, M.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2250. (i) Patz, M.; Mayr, H.; Bartl, J.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 490. (j) Mayr, H.; Gorath, G. J. Am. Chem. Soc. 1995, 117, 7862. (k) Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938. (l) Mayr, H.; Rau, D. Chem. Ber. 1994, 127, 2493. (m) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900. (n) Burfeindt, J; Patz, M.; Müller, M.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 3629.
54. For examples in radical chemistry, see: (a) Small, R. D., Jr.; Scaiano, J. C. J. Phys. Chem. 1977, 81, 828. (b) Newcomb, M.; Tanaka, N.; Bouvier, A.; Tronche, C.; Horner, J. H.; Musa, O. M.; Martinez, F. N. J. Am. Chem. Soc. 1996, 118, 8505.
55. For examples in radical chemistry, see: (a) Small, R. D., Jr.; Scaiano, J. C. J. Phys. Chem. 1977, 81, 828. (b) Newcomb, M.; Tanaka, N.; Bouvier, A.; Tronche, C.; Horner, J. H.; Musa, O. M.; Martinez, F. N. J. Am. Chem. Soc. 1996, 118, 8505.
56. The pyridine probe method has been used extensively to investigate the reaction dynamics of carbenes which lack useful UV-visible chromophores. See: (a) Platz, M. S.; Modarelli, D. A.; Morgan, S.; White, W. R.; Mullins, M.; Celebi, S.; Toscano, J. P. Progress in Reaction Kinetics; Rodgers, M. A., Ed.; Elsevier, 1994, 19, 93. (b) Platz, M. S.; White, W. R., III; Modarelli, D. A.; Celebi, S. A. Res. Chem. Intermed. 1994, 175. (c) Jackson, J. E.; Platz, M. S. In Advances in Carbene Chemistry; Brinker, U., Ed.; JAI Press: Greenwich, CT, 1994, Vol. 1, p 89, and references within.
57. The pyridine probe method has been used extensively to investigate the reaction dynamics of carbenes which lack useful UV-visible chromophores. See: (a) Platz, M. S.; Modarelli, D. A.; Morgan, S.; White, W. R.; Mullins, M.; Celebi, S.; Toscano, J. P. Progress in Reaction Kinetics; Rodgers, M. A., Ed.; Elsevier, 1994, 19, 93. (b) Platz, M. S.; White, W. R., III; Modarelli, D. A.; Celebi, S. A. Res. Chem. Intermed. 1994, 175. (c) Jackson, J. E.; Platz, M. S. In Advances in Carbene Chemistry; Brinker, U., Ed.; JAI Press: Greenwich, CT, 1994, Vol. 1, p 89, and references within.
58. The pyridine probe method has been used extensively to investigate the reaction dynamics of carbenes which lack useful UV-visible chromophores. See: (a) Platz, M. S.; Modarelli, D. A.; Morgan, S.; White, W. R.; Mullins, M.; Celebi, S.; Toscano, J. P. Progress in Reaction Kinetics; Rodgers, M. A., Ed.; Elsevier, 1994, 19, 93. (b) Platz, M. S.; White, W. R., III; Modarelli, D. A.; Celebi, S. A. Res. Chem. Intermed. 1994, 175. (c) Jackson, J. E.; Platz, M. S. In Advances in Carbene Chemistry; Brinker, U., Ed.; JAI Press: Greenwich, CT, 1994, Vol. 1, p 89, and references within.
59. Pezacki, J. P.; Wagner, B. D.; Lew, C. S. Q.; Warkentin, J.; Lusztyk, J. J. Am. Chem. Soc. 1997, 119, 1789.
60. Oxadiazoline precursors have also been used to study dialkyl and cycloalkylcarbenes in solution: (a) Pezacki, J. P.; Pole, D. L.; Warkentin, J.; Chen, T.; Ford, F.; Toscano, J.; Fell, J.; Platz, M. S. J. Am. Chem. Soc. 1997, 119, 3191. (b) Pezacki, J. P.; Wood, P. D.; Gadosy, T. A.; Lusztyk, J.; Warkentin, J. J. Am. Chem. Soc. 1998, 120, 8681. (c) Pezacki, J. P.; Warkentin, J.; Wood, P. D.; Lusztyk, J.; Yuzawa, T.; Gudmundsdottir, A. D.; Morgan, S.; Platz, M. S. J. Photochem. Photobiol. A Chem. 1998, 116, 1. (d) Pezacki, J. P.; Couture, P.; Dunn, J. A.; Warkentin, J.; Wood, P. D.; Lusztyk, J.; Ford, F.; Platz, M. S. J. Org. Chem. 1999, 64, 4456.
61. Oxadiazoline precursors have also been used to study dialkyl and cycloalkylcarbenes in solution: (a) Pezacki, J. P.; Pole, D. L.; Warkentin, J.; Chen, T.; Ford, F.; Toscano, J.; Fell, J.; Platz, M. S. J. Am. Chem. Soc. 1997, 119, 3191. (b) Pezacki, J. P.; Wood, P. D.; Gadosy, T. A.; Lusztyk, J.; Warkentin, J. J. Am. Chem. Soc. 1998, 120, 8681. (c) Pezacki, J. P.; Warkentin, J.; Wood, P. D.; Lusztyk, J.; Yuzawa, T.; Gudmundsdottir, A. D.; Morgan, S.; Platz, M. S. J. Photochem. Photobiol. A Chem. 1998, 116, 1. (d) Pezacki, J. P.; Couture, P.; Dunn, J. A.; Warkentin, J.; Wood, P. D.; Lusztyk, J.; Ford, F.; Platz, M. S. J. Org. Chem. 1999, 64, 4456.
62. Oxadiazoline precursors have also been used to study dialkyl and cycloalkylcarbenes in solution: (a) Pezacki, J. P.; Pole, D. L.; Warkentin, J.; Chen, T.; Ford, F.; Toscano, J.; Fell, J.; Platz, M. S. J. Am. Chem. Soc. 1997, 119, 3191. (b) Pezacki, J. P.; Wood, P. D.; Gadosy, T. A.; Lusztyk, J.; Warkentin, J. J. Am. Chem. Soc. 1998, 120, 8681. (c) Pezacki, J. P.; Warkentin, J.; Wood, P. D.; Lusztyk, J.; Yuzawa, T.; Gudmundsdottir, A. D.; Morgan, S.; Platz, M. S. J. Photochem. Photobiol. A Chem. 1998, 116, 1. (d) Pezacki, J. P.; Couture, P.; Dunn, J. A.; Warkentin, J.; Wood, P. D.; Lusztyk, J.; Ford, F.; Platz, M. S. J. Org. Chem. 1999, 64, 4456.
63. Oxadiazoline precursors have also been used to study dialkyl and cycloalkylcarbenes in solution: (a) Pezacki, J. P.; Pole, D. L.; Warkentin, J.; Chen, T.; Ford, F.; Toscano, J.; Fell, J.; Platz, M. S. J. Am. Chem. Soc. 1997, 119, 3191. (b) Pezacki, J. P.; Wood, P. D.; Gadosy, T. A.; Lusztyk, J.; Warkentin, J. J. Am. Chem. Soc. 1998, 120, 8681. (c) Pezacki, J. P.; Warkentin, J.; Wood, P. D.; Lusztyk, J.; Yuzawa, T.; Gudmundsdottir, A. D.; Morgan, S.; Platz, M. S. J. Photochem. Photobiol. A Chem. 1998, 116, 1. (d) Pezacki, J. P.; Couture, P.; Dunn, J. A.; Warkentin, J.; Wood, P. D.; Lusztyk, J.; Ford, F.; Platz, M. S. J. Org. Chem. 1999, 64, 4456.
64. -1) as the monitoring source was used. Wagner, B. D.; Arnold, B. R.; Brown, G. S.; Lusztyk, J. J. Am. Chem. Soc. 1998, 120, 1827. For a description of laser flash photolysis with UV-vis detection, see: Kazanis, S.; Azarani, A.; Johnston, L. J. J. Phys. Chem. 1991, 95, 4430.
65. -1) as the monitoring source was used. Wagner, B. D.; Arnold, B. R.; Brown, G. S.; Lusztyk, J. J. Am. Chem. Soc. 1998, 120, 1827. For a description of laser flash photolysis with UV-vis detection, see: Kazanis, S.; Azarani, A.; Johnston, L. J. J. Phys. Chem. 1991, 95, 4430.
66. 8-11
67. McClelland, R. A.; Chan. C.; Cozens, F.; Modro, A.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1991, 30, 1337.
68. (a) McClelland, R. A.; Cozens, F. L.; Li, J.; Steenken, S. J. Chem. Soc., Perkin Trans. 2 1996, 1531.
69. (b) Cozens, F. L.; Mathivanan, N.; McClelland, R. A.; Steenken, S. J. Chem. Soc., Perkin Trans. 2 1992, 2083.
70. (c) Cozens, F. L.; Li, J.; McClelland, R. A.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1992, 31, 743.
71. (d) McClelland, R. A.; Mathivanan, N.; Steenken, S. J. Am. Chem. Soc. 1990, 112, 4857.
72. Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 958.
73. (a) Steenken, S.; McClelland, R. A. J. Am. Chem. Soc. 1990, 112, 9648.
74. (b) Mathivanan, N.; Cozens, F.; McClelland, R. A.; Steenken, S. J. Am. Chem. Soc. 1992, 114, 2198.
75. (c) Lew, C. S. Q.; McClelland, R. A. J. Am. Chem. Soc. 1993, 115, 11516.
76. Cozens, F.; Li, J.; McClelland, R. A.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1992, 31, 743.
77. Platz, M. S.; Modarelli, D. A.; Morgan, S.; White, W. R.; Mullins, M.; Celebi, S.; Toscano, J. P. Progress in Reaction Kinetics; Rodgers, M. A., Ed.; Elsevier: New York, 1994, 19, 93, and references therein.
78. Richard, J. P.; Rothenberg, M. E.; Jencks, W. P. J. Am. Chem. Soc. 1984, 106, 1361.
79. Richard, J. P.; Jencks, W. P. J. Am. Chem. Soc. 1984, 106, 1373.
80. Richard, J. P.; Jencks, W. P. J. Am. Chem. Soc. 1982, 104, 4691.
81. McClelland, R. A.; Kanagasabapathy, V. M.; Banait, N. S.; Steenken, S. J. Am. Chem. Soc. 1991, 113, 1009.
82. Mazur, R.H.; White, W.N.; Semenow, D.A.; Lee, C.-C.; Silver, M.S.; Roberts, J.D. J. Am. Chem. Soc. 1959, 81, 4390.
83. 2.
84. 2 as a neutral leaving group: Toteva, M. M.; J. P. Richard J. Am. Chem. Soc. 1996, 118, 11434.
85. For analogous reactions, see: (a) Gassman, P. G.; Talley, J. J. J. Am. Chem. Soc. 1980, 102, 1214. (b) Gassman, P. G.; Talley, J. J. J. Am. Chem. Soc. 1980, 102, 4138. (c) Gassman, P. G.; Saito, K; Talley, J. J. J. Am. Chem. Soc. 1980, 102, 7613.
86. For analogous reactions, see: (a) Gassman, P. G.; Talley, J. J. J. Am. Chem. Soc. 1980, 102, 1214. (b) Gassman, P. G.; Talley, J. J. J. Am. Chem. Soc. 1980, 102, 4138. (c) Gassman, P. G.; Saito, K; Talley, J. J. J. Am. Chem. Soc. 1980, 102, 7613.
87. For analogous reactions, see: (a) Gassman, P. G.; Talley, J. J. J. Am. Chem. Soc. 1980, 102, 1214. (b) Gassman, P. G.; Talley, J. J. J. Am. Chem. Soc. 1980, 102, 4138. (c) Gassman, P. G.; Saito, K; Talley, J. J. J. Am. Chem. Soc. 1980, 102, 7613.
88. Cozens, F.; Li, J.; McClelland, R. A.; Steenken, S. Angew. Chem., Int. Ed. Engl. 1992, 31, 743.
89. Yields were variable and were as high as 90% depending on the solvent and [TMB]. Exact yields were not determined. Products containing trifluoroacetate groups were unstable to GC conditions and different yields were obtained with various column conditions.
90. Richard, J. P. Tetrahedron 1995, 51, 1535.
91. Jencks, W. P. Chem. Soc. Rev. 1981, 10, 345.
92. Olah, G. A. Acc. Chem. Res. 1971, 4, 420.
93. Ma, J. C.; Dougherty, D. A. Chem. Rev. 1997, 97, 1303.
94. Moss, R. A.; Yan, S.; Krogh-Jespersen, K. J. Am. Chem. Soc. 1998, 120, 1088.
95. (a) Roberts, D. D. J. Org. Chem. 1984, 49, 2521.
96. (b) Bentley, T. W.; Bowen, C. T.; Brown, H. C.; Chloupek, F. J. J. Org. Chem. 1981, 46, 38.
97. (c) Peters, E. N. J. Am. Chem. Soc. 1976, 98, 5627.
98. (d) Roberts, D. D. J. Org. Chem. 1971, 37, 1510.
99. (e) Bentley, T. W.; Jurczyk, S.; Roberts, K. J. Chem. Soc., Perkin Trans. 2 1987, 293.
100. (f) Gassman, P. G.; Saito, K. Tetrahedron Lett. 1981, 1311.
101. (g) Ando, T.; Tsukamoto, S. Tetrahedron Lett. 1977, 2775.
102. (h) Creary, X.; Geiger, C. C. J. Am. Chem. Soc. 1982, 104, 4151.
103. (i) Fry, J. L.; Lancelot, C. J.; Lam, L. K. M.; Harris, J. M.; Bingham, R. C.; Raber, D. J.; Hall, R. E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1970, 92, 2538.
104. (j) Fry, J. L.; Harris, J. M.; Bingham, R. C.; Schleyer, P. v. R. J. Am. Chem. Soc. 1970, 92, 2540.
105. (k) Schleyer, P. v. R.; Fry, J. L.; Lam, L. K. M.; Lancelot, C. J. J. Am. Chem. Soc. 1970, 92, 2542.
106. Raber, D. J.; Harris, J. M.; Hall, R. E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1971, 93, 4821, and references therein.
107. (a) Olah, G. A.; Reddy, V. P.; Prakash, G. K. S. Chem. Rev. 1992, 92, 69.
108. (b) Richey, H. G., Jr. In Carbonium ions; Olah, G. A., Schleyer, P. v. R., Eds.; Wiley-Interscience: New York, 1972; Vol. III, p 1201.
109. (c) Wiberg, K. B.; Hess, A., Jr.; Ashe, A. J., III In Carbonium ions; Olah, G. A.; Schleyer, P. v. R., Eds.; Wiley-Interscience: New York, 1972; Vol. III, p 1295.
110. Cyclopropyl groups adjacent to carbocations have been shown by X-ray crystallography to adopt bisecting conformations in several analogues. See: (a) Childs, R. F.; Kostyk, M. D.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1990, 112, 8912. (b) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1986, 108, 3613. (c) Chadda, S. K.; Childs, R. F.; Faggiani, R.; Lock, C. J. L. J. Am. Chem. Soc. 1986, 108, 1694. (d) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M.; Zweep, S. D. J. Am. Chem. Soc. 1986, 108, 1692. (e) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Varadarajan, A. Acta. Crystallogr. 1984, C40, 1291. (f) Childs, R. F.; Varadarajan, A.; Lock, C. J. L.; Faggiani, R.; Fyfe, C. A.; Wasylishen, R. E. J. Am. Chem. Soc. 1982, 104, 2452.
111. Cyclopropyl groups adjacent to carbocations have been shown by X-ray crystallography to adopt bisecting conformations in several analogues. See: (a) Childs, R. F.; Kostyk, M. D.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1990, 112, 8912. (b) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1986, 108, 3613. (c) Chadda, S. K.; Childs, R. F.; Faggiani, R.; Lock, C. J. L. J. Am. Chem. Soc. 1986, 108, 1694. (d) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M.; Zweep, S. D. J. Am. Chem. Soc. 1986, 108, 1692. (e) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Varadarajan, A. Acta. Crystallogr. 1984, C40, 1291. (f) Childs, R. F.; Varadarajan, A.; Lock, C. J. L.; Faggiani, R.; Fyfe, C. A.; Wasylishen, R. E. J. Am. Chem. Soc. 1982, 104, 2452.
112. Cyclopropyl groups adjacent to carbocations have been shown by X-ray crystallography to adopt bisecting conformations in several analogues. See: (a) Childs, R. F.; Kostyk, M. D.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1990, 112, 8912. (b) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1986, 108, 3613. (c) Chadda, S. K.; Childs, R. F.; Faggiani, R.; Lock, C. J. L. J. Am. Chem. Soc. 1986, 108, 1694. (d) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M.; Zweep, S. D. J. Am. Chem. Soc. 1986, 108, 1692. (e) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Varadarajan, A. Acta. Crystallogr. 1984, C40, 1291. (f) Childs, R. F.; Varadarajan, A.; Lock, C. J. L.; Faggiani, R.; Fyfe, C. A.; Wasylishen, R. E. J. Am. Chem. Soc. 1982, 104, 2452.
113. Cyclopropyl groups adjacent to carbocations have been shown by X-ray crystallography to adopt bisecting conformations in several analogues. See: (a) Childs, R. F.; Kostyk, M. D.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1990, 112, 8912. (b) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1986, 108, 3613. (c) Chadda, S. K.; Childs, R. F.; Faggiani, R.; Lock, C. J. L. J. Am. Chem. Soc. 1986, 108, 1694. (d) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M.; Zweep, S. D. J. Am. Chem. Soc. 1986, 108, 1692. (e) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Varadarajan, A. Acta. Crystallogr. 1984, C40, 1291. (f) Childs, R. F.; Varadarajan, A.; Lock, C. J. L.; Faggiani, R.; Fyfe, C. A.; Wasylishen, R. E. J. Am. Chem. Soc. 1982, 104, 2452.
114. Cyclopropyl groups adjacent to carbocations have been shown by X-ray crystallography to adopt bisecting conformations in several analogues. See: (a) Childs, R. F.; Kostyk, M. D.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1990, 112, 8912. (b) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1986, 108, 3613. (c) Chadda, S. K.; Childs, R. F.; Faggiani, R.; Lock, C. J. L. J. Am. Chem. Soc. 1986, 108, 1694. (d) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M.; Zweep, S. D. J. Am. Chem. Soc. 1986, 108, 1692. (e) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Varadarajan, A. Acta. Crystallogr. 1984, C40, 1291. (f) Childs, R. F.; Varadarajan, A.; Lock, C. J. L.; Faggiani, R.; Fyfe, C. A.; Wasylishen, R. E. J. Am. Chem. Soc. 1982, 104, 2452.
115. Cyclopropyl groups adjacent to carbocations have been shown by X-ray crystallography to adopt bisecting conformations in several analogues. See: (a) Childs, R. F.; Kostyk, M. D.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1990, 112, 8912. (b) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M. J. Am. Chem. Soc. 1986, 108, 3613. (c) Chadda, S. K.; Childs, R. F.; Faggiani, R.; Lock, C. J. L. J. Am. Chem. Soc. 1986, 108, 1694. (d) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Mahendran, M.; Zweep, S. D. J. Am. Chem. Soc. 1986, 108, 1692. (e) Childs, R. F.; Faggiani, R.; Lock, C. J. L.; Varadarajan, A. Acta. Crystallogr. 1984, C40, 1291. (f) Childs, R. F.; Varadarajan, A.; Lock, C. J. L.; Faggiani, R.; Fyfe, C. A.; Wasylishen, R. E. J. Am. Chem. Soc. 1982, 104, 2452.
116. (a) Wolf, J. F.; Harch, P. G.; Taft, R. W.; Hehre, W. J. J. Am. Chem. Soc. 1975, 97, 2902.
117. (b) Taft, R. W.; Martin, R. H.; Lampe, J. Am. Chem. Soc. 1965, 87, 2490.
118. (c) Deno, N. C.; Richey, H. G., Jr.; Liu, J. S.; Lincoln, D. N.; Turner, J. D. J. Am. Chem. Soc. 1965, 87, 4533.
119. (a) Moss, R. A.; Shen, S.; Jespersen, K. K.; Potenza, J. A.; Schugar, H.-J.; Munjal, R. C. J. Am. Chem. Soc. 1986, 108, 134.
120. (b) Kerber, R. C.; Hsu, C.-M. J. Am. Chem. Soc. 1973, 95, 3239.
121. 2 is δ 254.2. See: (a) Olah, G. A.; Prakash, G. K. S.; Liang, G. J. Org. Chem. 1977, 42, 2666.
122. (b) Olah, G. A.; White, A. M. J. Am. Chem. Soc. 1969, 91, 5801.
123. Kirmse, W.; Krzossa, B.; Steenken, S. J. Am. Chem. Soc. 1996, 118, 7473.
124. 55d
125. Marcus, R. A. J. Phys. Chem. 1968, 72, 891.
126. Steenken, S.; Ashokkumar, M.; Maruthamuthu, P.; McClelland, R. A. J. Am. Chem. Soc. 1998, 120, 11925.
127. HFIP = 140.
128. Phenyldiazonium ions are stable and isolable species in solution whereas sec-alkanediazonium ions, such as 2-propanediazonium ion, decompose spontaneously and have never been observed directly. See ref 10f.
129. Personal communication from R. A. McClelland.
130. Glaser, R.; Horan, C. J.; Lewis, M.; Zollinger, H. J. Org. Chem. 1999, 64, 902.
131. It is possible that the least reactive alkanediazonium ions may live long enough to allow for partial diffusional separation from the least coordinating trifluoroacetate counterion.
132. Wurdeman, R. L.; Church, K. M.; Gold, B. J. Am. Chem. Soc. 1989, 111, 6408.
133. (a) Singer, B. Prog. Nucl. Acids Res. Mol. Biol. 1975, 15, 219, and 330.
134. (b) Singer, B. Nature 1976, 264, 333.
135. Antrub, H.; Stoner, G. D. Cancer Res. 1982, 42, 1307.