The methoxymethyl cation cleaves peptide bonds in the gas phase

(Note: The full text of this document is currently only available in the PDF Version )

Michael A. Freitas, Richard A. J. O’Hair, Suresh Dua and John H. Bowie


Abstract

Methoxymethyl cations and simple N-acyl amino acids and dipeptides react in the gas phase to form [M + MeOCH2]+ ions which fragment via a number of pathways including amide bond cleavage.


References

  1. M. A. Freitas, R. A. J. O'Hair, J. A. R. Schmidt, S. E. Tichy, B. E. Plashko and T. D. Williams, J. Mass Spectrom., 1996, 31, 1086 CrossRef CAS.
  2. For gas phase reactions of MeOCH2+ with glycine and cysteine, see (a) R. A. J. O'Hair, M. A. Freitas, S. Gronert, J. A. R. Schmidt and T. D. Williams, J. Org. Chem., 1995, 60, 1990 CrossRef CAS; (b) M. A. Freitas, R. A. J. O'Hair and T. D. Williams, submitted to J. Org. Chem. Search PubMed.
  3. Sequencing of Proteins and Peptides, in Laboratory Techniques in Biochemistry and Molecular Biology, 2nd edn., ed. G. Allen, Elsevier, Amsterdam, 1989, ch. 6 Search PubMed.
  4. Mass spectrom etry has been used to sequence small peptides. For some leading references, see (a) K. Biemann and I. A. Papayannopoulos, Acc. Chem. Res., 1994, 27, 370 CrossRef; (b) R. J. Waugh and J. H. Bowie, Rapid Commun. Mass Spectrom., 1994, 8, 169 CAS.
  5. The only other report of a peptide bond cleavage reaction involved reacting the [M – H] ion of some peptide models [MeC(O)NHCH2C(O)X; X = OEt and NHMe] with a neutral electrophile: X. Cheng and J. J. Grabowski, Proceedings of the 39th ASMS Conference on Mass Spectrometry and Allied Topics, Nashville, Tennesee, May 19–24, 1991, p. 477 Search PubMed.
  6. The methoxymethyl cation cleaves the acyl bond in acids, esters and amides: M. C. Caserio and J. K. Kim, J. Org. Chem., 1982, 47, 2940 Search PubMed.
  7. K. L. Busch, G. L. Glish and S. A. McLuckey, Mass Spectrometry/Mass Spectrometry. Techniques and Applications of Tandem Mass Spectrometry, VCH, New York, 1988 Search PubMed.
  8. H. E. Audier, F. Dahhani, A. Millet and D. Kuck, Chem. Commun., 1997, 429 RSC.
  9. K. Zhang, D. M. Zimmerman, A. Chung-Phillips and C. J. Cassady, J. Am. Chem. Soc., 1993, 115, 10 812 CrossRef CAS.
  10. See for example: J. P. Speir and I. J. Amster, J. Am. Soc. Mass Spectrom., 1995, 6, 1069 Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.