A study of the gas-phase reactivity of neutral alkoxy radicals by mass spectrometry: α-Cleavages and Barton-type hydrogen migrations

Chemistry - A European Journal

Volumn 3, Issue 11, 1997, Pages 1866-1883

  Hornung, Georg ^a   Schalley, Christoph A ^a   Dieterle, Martin ^a   Schröder, Detlef ^a   Schwarz, Helmut ^a  

^a TECHNISCHE UNIVERSITÄT BERLIN   (Germany)

Author keywords

Alkoxy radicals; Barton reaction; Density functional calculations; Mass spectrometry; Radicals

Indexed keywords

EID: 0030729810     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.19970031120     Document Type: Article

References (142)

1. For the original publication and reviews, see: a) D. H. R. Barton, J. M. Beaton, L. E. Geller, M. M. Pechet, J. Am. Chem. Soc. 1961, 83, 4076; b) D. H. R. Barton, Pure Appl. Chem. 1968, 16, 1; c) R. H. Hesse, Adv. Free-Radical Chem. 1969, 3, 83; d) D. H. R. Barton, R. H. Hesse, M. M. Pechet, L. Smith, J. Chem. Soc. Perkin Trans. 1979, 1, 1159; e) A. L. J. Beckwith, K. U. Ingold, Rearrangements in Ground and Excited States (Ed.: P. DeMayo), Vol. 1, Academic Press, New York, 1980, p. 251; f) W. Carruthers, Some Modern Methods of Organic Synthesis, 3rd ed., Cambridge University Press, Cambridge, 1992, p. 263.
2. For the original publication and reviews, see: a) D. H. R. Barton, J. M. Beaton, L. E. Geller, M. M. Pechet, J. Am. Chem. Soc. 1961, 83, 4076; b) D. H. R. Barton, Pure Appl. Chem. 1968, 16, 1; c) R. H. Hesse, Adv. Free-Radical Chem. 1969, 3, 83; d) D. H. R. Barton, R. H. Hesse, M. M. Pechet, L. Smith, J. Chem. Soc. Perkin Trans. 1979, 1, 1159; e) A. L. J. Beckwith, K. U. Ingold, Rearrangements in Ground and Excited States (Ed.: P. DeMayo), Vol. 1, Academic Press, New York, 1980, p. 251; f) W. Carruthers, Some Modern Methods of Organic Synthesis, 3rd ed., Cambridge University Press, Cambridge, 1992, p. 263.
3. For the original publication and reviews, see: a) D. H. R. Barton, J. M. Beaton, L. E. Geller, M. M. Pechet, J. Am. Chem. Soc. 1961, 83, 4076; b) D. H. R. Barton, Pure Appl. Chem. 1968, 16, 1; c) R. H. Hesse, Adv. Free-Radical Chem. 1969, 3, 83; d) D. H. R. Barton, R. H. Hesse, M. M. Pechet, L. Smith, J. Chem. Soc. Perkin Trans. 1979, 1, 1159; e) A. L. J. Beckwith, K. U. Ingold, Rearrangements in Ground and Excited States (Ed.: P. DeMayo), Vol. 1, Academic Press, New York, 1980, p. 251; f) W. Carruthers, Some Modern Methods of Organic Synthesis, 3rd ed., Cambridge University Press, Cambridge, 1992, p. 263.
4. For the original publication and reviews, see: a) D. H. R. Barton, J. M. Beaton, L. E. Geller, M. M. Pechet, J. Am. Chem. Soc. 1961, 83, 4076; b) D. H. R. Barton, Pure Appl. Chem. 1968, 16, 1; c) R. H. Hesse, Adv. Free-Radical Chem. 1969, 3, 83; d) D. H. R. Barton, R. H. Hesse, M. M. Pechet, L. Smith, J. Chem. Soc. Perkin Trans. 1979, 1, 1159; e) A. L. J. Beckwith, K. U. Ingold, Rearrangements in Ground and Excited States (Ed.: P. DeMayo), Vol. 1, Academic Press, New York, 1980, p. 251; f) W. Carruthers, Some Modern Methods of Organic Synthesis, 3rd ed., Cambridge University Press, Cambridge, 1992, p. 263.
5. For the original publication and reviews, see: a) D. H. R. Barton, J. M. Beaton, L. E. Geller, M. M. Pechet, J. Am. Chem. Soc. 1961, 83, 4076; b) D. H. R. Barton, Pure Appl. Chem. 1968, 16, 1; c) R. H. Hesse, Adv. Free-Radical Chem. 1969, 3, 83; d) D. H. R. Barton, R. H. Hesse, M. M. Pechet, L. Smith, J. Chem. Soc. Perkin Trans. 1979, 1, 1159; e) A. L. J. Beckwith, K. U. Ingold, Rearrangements in Ground and Excited States (Ed.: P. DeMayo), Vol. 1, Academic Press, New York, 1980, p. 251; f) W. Carruthers, Some Modern Methods of Organic Synthesis, 3rd ed., Cambridge University Press, Cambridge, 1992, p. 263.
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27. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
28. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
29. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
30. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
31. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
32. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
33. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
34. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
35. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
36. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
37. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; l) N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
38. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
39. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
40. For reviews dealing with NR techniques, see: a) G. I. Gellene, R. F. Porter, Acc. Chem. Res. 1983, 16, 200; b) C. Wesdemiotis, F. W. McLafferty, Chem. Rev. 1987, 87, 485; c) J. K. Terlouw, H. Schwarz, Angew. Chem. 1987, 99, 829; Angew. Chem. Int. Ed. Engl. 1987, 26, 805; d) J. L. Holmes, Mass Spectrom. Rev. 1989, 8, 513; e) J. L. Holmes, Adv. Mass Spectrom. 1989, 11, 53; f) J. K. Terlouw, ibid. 1989, 11, 984; g) A. W. McMahon, S. K. Chowdhury, A. G. Harrison, Org. Mass Spectrom. 1989, 24, 620; h) H. Schwarz, Pure Appl. Chem. 1989, 61, 685; i) F. W. McLafferty, Science 1990, 247, 925; j) F. W. McLafferty, Int. J. Mass Spectrom. Ion Processes 1992, 118/119, 221; k) F. Turecek, Org. Mass Spectrom. 1992, 27, 1087; N. Goldberg, H. Schwarz, Acc. Chem. Res. 1994, 27, 347; m) D. V. Zagorevskii, J. L. Holmes, Mass Spectrom. Rev. 1994, 13, 133; n) M. J. Polce, Š. Beranová, M. J. Nold, C. Wesdemiotis, J. Mass Spectrom. 1996, 31, 1073; o) C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Chem. Soc. Rev., submitted for publication.
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60. Differences between NR and CR mass spectra have earlier been attributed to neutral reactivity. See, for example: a) P. E. O'Bannon, D. Sülzle, W. P. Dailey, H. Schwarz, J. Am. Chem. Soc. 1992, 114, 344; b) D. Schröder, C. A. Schalley, N. Goldberg, J. Hrušák, H. Schwarz, Chem. Eur. J. 1996, 2, 1235; c) C. A. Schalley, A. Fiedler, G. Hornung, R. Wesendrup, D. Schröder, H. Schwarz, ibid. 1997, 3, 626; d) C. A. Schalley, Ph.D. Thesis, Technische Universität Berlin, D83, 1997.
61. Differences between NR and CR mass spectra have earlier been attributed to neutral reactivity. See, for example: a) P. E. O'Bannon, D. Sülzle, W. P. Dailey, H. Schwarz, J. Am. Chem. Soc. 1992, 114, 344; b) D. Schröder, C. A. Schalley, N. Goldberg, J. Hrušák, H. Schwarz, Chem. Eur. J. 1996, 2, 1235; c) C. A. Schalley, A. Fiedler, G. Hornung, R. Wesendrup, D. Schröder, H. Schwarz, ibid. 1997, 3, 626; d) C. A. Schalley, Ph.D. Thesis, Technische Universität Berlin, D83, 1997.
62. Differences between NR and CR mass spectra have earlier been attributed to neutral reactivity. See, for example: a) P. E. O'Bannon, D. Sülzle, W. P. Dailey, H. Schwarz, J. Am. Chem. Soc. 1992, 114, 344; b) D. Schröder, C. A. Schalley, N. Goldberg, J. Hrušák, H. Schwarz, Chem. Eur. J. 1996, 2, 1235; c) C. A. Schalley, A. Fiedler, G. Hornung, R. Wesendrup, D. Schröder, H. Schwarz, ibid. 1997, 3, 626; d) C. A. Schalley, Ph.D. Thesis, Technische Universität Berlin, D83, 1997.
63. A detailed description of the method will appear soon in which several methodological problems only briefly mentioned here will be discussed explicitly: C. A. Schalley, G. Hornung, D. Schröder, H. Schwarz, Int. J. Mass Spectrom. Ion Processes, in press.
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106. R. S. Mercer, A. G. Harrison, Can. J. Chem. 1988, 66, 2947, and references cited therein.
107. D. P. Stevenson, Discuss. Faraday Soc. 1951, 10, 35.
108. 8 isomers listed in ref. [24] have ionization energies of more than 9 eV.
109. Several previous studies provided experimental and theoretical evidence for a remarkably high regioselectivity of this process, which is due not only to enthalpic but also to entropic effects. For examples, see refs. [1,5,14].
110. For a discussion of the role of bent hydrogen bonds in proton transfers, see: S. Scheiner, Acc. Chem. Res. 1994, 27, 402.
111. Rearrangement reactions in reionized cations stemming from charge reversal or neutralization reionization experiments are, of course, known and have previously been described. See, for example: N. Goldberg, A. Fiedler, H. Schwarz, J. Phys. Chem. 1995, 99, 15334, and references therein.
112. a) D. F. McMillen, D. M. Golden, Ann. Rev. Phys. Chem. 1982, 33, 493;
113. b) J. March, Advanced Organic Chemistry, 4th ed., Wiley, New York, 1992, p.24.
114. -1 for the hydrogen transfer in the Barton reaction is discussed in: C. Wentrup, Reaktive Zwischenstufen I, Thieme, Stuttgart, 1979.
115. J. W. Wilt, Free Radicals, Vol. 1 (Ed.: J. K. Kochi), Wiley, New York, 1973, p. 333.
116. ., may also be due to contributions of collision processes following the 1,5-hydrogen migration.
117. S. Dua, G. W. Adams, J. C. Sheldon, J. H. Bowie, J. Chem. Soc. Perkin Trans. 2 1996, 1251.
118. K. N. Houk, Y. Li, J. D. Evanseck, Angew. Chem. Int. Ed. Engl. 1992, 31, 682.
119. a) D. J. McAdoo, F. W. McLafferty, P. F. Bente, III, J. Am. Chem. Soc. 1972, 94, 2027;
120. b) W. Koch, P. v. R. Schleyer, P. Buzek, B. Liu, Croat. Chim. Acta 1992, 65, 655.
121. a) T. H. Morton, Tetrahedron 1982, 38, 3195;
122. b) N. Heinrich, H. Schwarz, Ion and Cluster Ion Spectroscopy and Structure (Ed.: J. P. Maier), Elsevier, Amsterdam, 1989, p. 329, and references therein;
123. c) R. D. Bowen, Acc. Chem. Res. 1991, 24, 364;
124. d) P. Longevialle, Mass Spectrom. Rev. 1992, 11, 157;
125. e) D. K. Böhme, Int. J. Mass Spectrom. Ion Processes 1992, 115, 95.
126. For applications of mass spectrometry to stereochemical problems in connection with the decay of metastable ions, see: a) Y. S. Nekrasov, D. V. Zagorevskii, Org. Mass Spectrom. 1991, 26, 733; b) T. Prüsse, A. Fiedler, H. Schwarz, Helv. Chim. Acta 1991, 74, 1127; c) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 1632; d) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 113; e) K. Seemeyer, H. Schwarz, ibid. 1993, 76, 2384; f) N. Raabe, S. Karrass, H. Schwarz, Chem. Ber. 1994, 127, 261; g) C. A. Schalley, D. Schröder, H. Schwarz, J. Am. Chem. Soc. 1994, 116, 11089; h) Applications of Mass Spectrometry to Organic Stereochemistry (Eds:. J. S. Splitter, F. Turecek), VCH, Weinheim, 1994; i) K. Schroeter, C. A. Schalley, R. Wesendrup, D. Schröder, H. Schwarz, Organometallics, 1997, 16, 986.
127. For applications of mass spectrometry to stereochemical problems in connection with the decay of metastable ions, see: a) Y. S. Nekrasov, D. V. Zagorevskii, Org. Mass Spectrom. 1991, 26, 733; b) T. Prüsse, A. Fiedler, H. Schwarz, Helv. Chim. Acta 1991, 74, 1127; c) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 1632; d) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 113; e) K. Seemeyer, H. Schwarz, ibid. 1993, 76, 2384; f) N. Raabe, S. Karrass, H. Schwarz, Chem. Ber. 1994, 127, 261; g) C. A. Schalley, D. Schröder, H. Schwarz, J. Am. Chem. Soc. 1994, 116, 11089; h) Applications of Mass Spectrometry to Organic Stereochemistry (Eds:. J. S. Splitter, F. Turecek), VCH, Weinheim, 1994; i) K. Schroeter, C. A. Schalley, R. Wesendrup, D. Schröder, H. Schwarz, Organometallics, 1997, 16, 986.
128. For applications of mass spectrometry to stereochemical problems in connection with the decay of metastable ions, see: a) Y. S. Nekrasov, D. V. Zagorevskii, Org. Mass Spectrom. 1991, 26, 733; b) T. Prüsse, A. Fiedler, H. Schwarz, Helv. Chim. Acta 1991, 74, 1127; c) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 1632; d) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 113; e) K. Seemeyer, H. Schwarz, ibid. 1993, 76, 2384; f) N. Raabe, S. Karrass, H. Schwarz, Chem. Ber. 1994, 127, 261; g) C. A. Schalley, D. Schröder, H. Schwarz, J. Am. Chem. Soc. 1994, 116, 11089; h) Applications of Mass Spectrometry to Organic Stereochemistry (Eds:. J. S. Splitter, F. Turecek), VCH, Weinheim, 1994; i) K. Schroeter, C. A. Schalley, R. Wesendrup, D. Schröder, H. Schwarz, Organometallics, 1997, 16, 986.
129. For applications of mass spectrometry to stereochemical problems in connection with the decay of metastable ions, see: a) Y. S. Nekrasov, D. V. Zagorevskii, Org. Mass Spectrom. 1991, 26, 733; b) T. Prüsse, A. Fiedler, H. Schwarz, Helv. Chim. Acta 1991, 74, 1127; c) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 1632; d) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 113; e) K. Seemeyer, H. Schwarz, ibid. 1993, 76, 2384; f) N. Raabe, S. Karrass, H. Schwarz, Chem. Ber. 1994, 127, 261; g) C. A. Schalley, D. Schröder, H. Schwarz, J. Am. Chem. Soc. 1994, 116, 11089; h) Applications of Mass Spectrometry to Organic Stereochemistry (Eds:. J. S. Splitter, F. Turecek), VCH, Weinheim, 1994; i) K. Schroeter, C. A. Schalley, R. Wesendrup, D. Schröder, H. Schwarz, Organometallics, 1997, 16, 986.
130. For applications of mass spectrometry to stereochemical problems in connection with the decay of metastable ions, see: a) Y. S. Nekrasov, D. V. Zagorevskii, Org. Mass Spectrom. 1991, 26, 733; b) T. Prüsse, A. Fiedler, H. Schwarz, Helv. Chim. Acta 1991, 74, 1127; c) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 1632; d) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 113; e) K. Seemeyer, H. Schwarz, ibid. 1993, 76, 2384; f) N. Raabe, S. Karrass, H. Schwarz, Chem. Ber. 1994, 127, 261; g) C. A. Schalley, D. Schröder, H. Schwarz, J. Am. Chem. Soc. 1994, 116, 11089; h) Applications of Mass Spectrometry to Organic Stereochemistry (Eds:. J. S. Splitter, F. Turecek), VCH, Weinheim, 1994; i) K. Schroeter, C. A. Schalley, R. Wesendrup, D. Schröder, H. Schwarz, Organometallics, 1997, 16, 986.
131. For applications of mass spectrometry to stereochemical problems in connection with the decay of metastable ions, see: a) Y. S. Nekrasov, D. V. Zagorevskii, Org. Mass Spectrom. 1991, 26, 733; b) T. Prüsse, A. Fiedler, H. Schwarz, Helv. Chim. Acta 1991, 74, 1127; c) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 1632; d) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 113; e) K. Seemeyer, H. Schwarz, ibid. 1993, 76, 2384; f) N. Raabe, S. Karrass, H. Schwarz, Chem. Ber. 1994, 127, 261; g) C. A. Schalley, D. Schröder, H. Schwarz, J. Am. Chem. Soc. 1994, 116, 11089; h) Applications of Mass Spectrometry to Organic Stereochemistry (Eds:. J. S. Splitter, F. Turecek), VCH, Weinheim, 1994; i) K. Schroeter, C. A. Schalley, R. Wesendrup, D. Schröder, H. Schwarz, Organometallics, 1997, 16, 986.
132. For applications of mass spectrometry to stereochemical problems in connection with the decay of metastable ions, see: a) Y. S. Nekrasov, D. V. Zagorevskii, Org. Mass Spectrom. 1991, 26, 733; b) T. Prüsse, A. Fiedler, H. Schwarz, Helv. Chim. Acta 1991, 74, 1127; c) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 1632; d) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 113; e) K. Seemeyer, H. Schwarz, ibid. 1993, 76, 2384; f) N. Raabe, S. Karrass, H. Schwarz, Chem. Ber. 1994, 127, 261; g) C. A. Schalley, D. Schröder, H. Schwarz, J. Am. Chem. Soc. 1994, 116, 11089; h) Applications of Mass Spectrometry to Organic Stereochemistry (Eds:. J. S. Splitter, F. Turecek), VCH, Weinheim, 1994; i) K. Schroeter, C. A. Schalley, R. Wesendrup, D. Schröder, H. Schwarz, Organometallics, 1997, 16, 986.
133. For applications of mass spectrometry to stereochemical problems in connection with the decay of metastable ions, see: a) Y. S. Nekrasov, D. V. Zagorevskii, Org. Mass Spectrom. 1991, 26, 733; b) T. Prüsse, A. Fiedler, H. Schwarz, Helv. Chim. Acta 1991, 74, 1127; c) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 1632; d) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 113; e) K. Seemeyer, H. Schwarz, ibid. 1993, 76, 2384; f) N. Raabe, S. Karrass, H. Schwarz, Chem. Ber. 1994, 127, 261; g) C. A. Schalley, D. Schröder, H. Schwarz, J. Am. Chem. Soc. 1994, 116, 11089; h) Applications of Mass Spectrometry to Organic Stereochemistry (Eds:. J. S. Splitter, F. Turecek), VCH, Weinheim, 1994; i) K. Schroeter, C. A. Schalley, R. Wesendrup, D. Schröder, H. Schwarz, Organometallics, 1997, 16, 986.
134. For applications of mass spectrometry to stereochemical problems in connection with the decay of metastable ions, see: a) Y. S. Nekrasov, D. V. Zagorevskii, Org. Mass Spectrom. 1991, 26, 733; b) T. Prüsse, A. Fiedler, H. Schwarz, Helv. Chim. Acta 1991, 74, 1127; c) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 1632; d) K. Seemeyer, T. Prüsse, H. Schwarz, ibid. 1993, 76, 113; e) K. Seemeyer, H. Schwarz, ibid. 1993, 76, 2384; f) N. Raabe, S. Karrass, H. Schwarz, Chem. Ber. 1994, 127, 261; g) C. A. Schalley, D. Schröder, H. Schwarz, J. Am. Chem. Soc. 1994, 116, 11089; h) Applications of Mass Spectrometry to Organic Stereochemistry (Eds:. J. S. Splitter, F. Turecek), VCH, Weinheim, 1994; i) K. Schroeter, C. A. Schalley, R. Wesendrup, D. Schröder, H. Schwarz, Organometallics, 1997, 16, 986.
135. a) D. Schröder, Ph.D. Thesis, Technische Universität Berlin, D 83, 1992;
136. b) D. Schröder, H. Schwarz, J. Am. Chem. Soc. 1993, 76, 8818;
137. c) G. Hornung, D. Schröder; H. Schwarz, ibid. 1995, 117, 8192;
138. d) G. Hornung, D. Schröder, H. Schwarz, ibid. 1997, 119, 2273.
139. The branching ratios are given without statistical corrections for the number of H/D atoms and neglecting the kinetic isotope effect, as their influence on the estimated value for the site selectivity is not significant.
140. D = 33/67 = 0.49 (9)
141. ., we obtain the following corrected values for the kinetic isotope and the steric effects: SE = 3.7 ± 1.3 and KIE = 1.5 ± 0. 3. Thus, the qualitative picture is not significantly altered by this side reaction.
142. 3 substituents in the C(3) position are interchanged.