Abstract
The selective functionaIization of C-H bonds remains one of the major focuses of catalytic and organic chemistry. High selectivity is often achieved by the presence of activating groups which induce the reactivity of the neighbouring C-H bonds by, for example, polarizing the bond, thus making the hydrogen more acidic, or by generally weakening the C-H bond. The selective functionalization of hydrocarbon segments of a molecule remote from any functional group represents a great challenge. While such reactions are common to enzymes which coordinate a functional group and geometrically select a specific section of the molecule (see, for example, the enzymatic conversion of stearic to oleic acid. Scheme 1), only a few cases in solution chemistry are reported [1] where a similar principle seems to be operative.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References and Notes
(a) R. Breslow, Chem. Soc. Rev. 1 (1972) 553. (b) R. Breslow, Acc. Chem. Res. 13 (1980) 170. (c) U. Kerb, M. Stahnke, P. E. Schulze and R. Wiechert, Angew. Chem. 93 (1981) 89.
a) J. Möller, Angew. Chem. Int. Ed. Engl. 11 (1972) 653. (b) J. L. Beauchamp, A. E. Stevens and R. R. Corderman, Pure Appl. Chem. 51 (1979) 976. (c) I. Gregor and M. Guilhaus, Mass Spectrom. Rev. 3 (1984) 39. (d) B. S. Freiser, Talanta 32 (1985) 697. (e) J. Allison, Prog. Inorg. Chem. 34 (1986) 627. (f) P. B. Armentrout in P. Ausloos and S. G. Lias (Eds.): Structure/Reactivity and Thermo-chemistry of Ions, D. Reidel, Dordrecht, 193 (1987) 97. (g) D. P. Ridge, ibid. 193 (1987) 165. (h) J. A. Simoes and J. L. Beauchamp, Chem. Rev, in preparation, (i) More than 100 References together with a detailed discussion of the gas-phase chemistry of gaseous aIkyne/iron (I) ion complexes may be found in: C. Schulze, H. Schwarz, D. A. Peake and M. L. Gross, J. Am. Chem. Soc. 109 (1987) 2318.
Selected references: (a) A. H. Janowicz, R. A. Periana, J. M. Buchanan, C. A. Kovac, J. M. Stryker, M. J. Wax and R. 6. Bergman, Pure Appl, Chem. 56 (1984) 13- (b). M. L. Green and D. O’Hare, Pure Appl. Chem. 57 (1985) 1897. (c) R. H. Crabtree, Chem. Rev. 85 (1985) 245. (d) J. Halpern, Inorq. Chim. Acta 100 (1985) 41. (e) I. P. Rothwell, Polyhedron 4 (1985) 77. (f) W. A. G. Graham, J. Organomet. Chem. 300 (1986) 81. (g) M. Brookhart and M. L. H. Green, J. Organomet. Chem. 250 (1983) 395.
For a description of the machine and its operation see: (a) T. Weiske, Ph.D. Thesis, Technical University Berlin, D 83 (1985). b) J. K. Terlouw, T. Weiske, H. Schwarz and J. L. Holmes, Org. Mass Spectrom. 21 (1986) 665.
T. Drewello, K. Eckart, C. B. Lebrilla and H. Schwarz, Int. J. Mass Spectrom. Ion Processes 76 (1987) 21.
Suggested structures are hypothetical in most cases studied in mass spectrometry. They are based on plausibility arguments using as much direct and indirect evidence available from experiments and model consideration. Nevertheless, their heuristic merits are undeniable in chemistry as long as speculations remain within acceptable limits. Similarly, the neutrals formed from the organometaIIic complexes are not structurally characterized but inferred indirectly from the mass differences between the mass-selected precursor ions and observed daughter ion. Fortunately, in many cases on energetic grounds there does not exist any doubt as to the actual structures of the neutrals (for example, Δm = 2 corresponds to H2, Δm = 16 to CH4, Δm = 28 to C2H4 etc.).
a) R. P. Cooks (Ed.): Collision Spectroscopy, Plenum Press, New York (1978). (b) K. Levsen and H. Schwarz, Mass Spectrom. Rev. 2. (1983) 77.
a) C. B. Lebrilla, C. Schulze and H. Schwarz, J. Am. Chem. Soc. 109 (1987) 98. (b) G. Czekay, T. Drewello and H. Schwarz, J. Am. Chem. Soc., submitted.
a) B. S. Larsen, D. P. Ridge, J. Am. Chem. Soc. 106 (1984) 1912. D. A. Peake, M. L. Gross, Anal. Chem. 57 (1985) 115.
(a) D. A. Peake and M. L. Gross, Organometallics 5 (1986) 1236. (b) See, however,: C. Schulze and H. Schwarz, Chimia 41 (1987) 29.
C. B. Lebrilla, T. Drewello and H. Schwarz, J. Am. Chem. Soc. 109 (1987) 5639.
C. B. Lebrilla, T. DrewelLo and H. Schwarz, Int, J. Mass Spectrom. Ion Processes 79 (1987) 287
(a) J.-Y. Saillard and R. Hoffmann, J. Am, Chem, Soc. 106 (1984) 2006. (b) C. B, Lebritla and W. F. Meier, Chem. Phys. Lett. 105 (1984) 183.
See, for example: P. L, Watson and D. C. Roe, J. Am. Chem. Soc. 104 (1982) 6471.
(a) P. B. Armentrout and J. L. Beauchamp, J. Am. Chem. Soc. 103 (1981) 784. (b) L. F. Halle, P. B. Armentrout and J. L. Beauchamp, Organometallics 1 (1982) 963. (c) R. Houriet, L. F Halle and J. L. Beauchamp, ibid. 2 (1983) 1818. (d) M. A. Tolbert and J. L. Beauchamp, ibid. 106 (1984) 8117. (e) R. Tonkyn, M. Ronan and J. C. Weishar, J. Phys. Chem. 92 (1988) 92.
T. Prüsse, C. B. Lebrilla, T. Drewello and H. Schwarz, J. Am. Chem. Soc. 110 (1988) 000.
T. Prüsse, T. Drewello, C. B. Lebrilla and H. Schwarz, J. Am. Chem. Soc., submitted.
C. B. Lebrilla, T. Drewello and H. Schwarz, Organometallics 6 (1987) 2450
For typical examples, see: (a) S. Patai (Ed.): The Chemistry of Functional Groups, Wiley, New York (1970). (b) U. Schöllkopf, Pure Appl. Chem. 51 (1979) 1347.
K. Eller, C. B. Lebrilla, T. Drewello and H. Schwarz, J. Am. Chem. Soc. 110 (1988) 3068.
P. B. Armentrout, L. F. Halle and J. L. Beauchamp, J. Am. Chem. Soc. 103 (1981) 6624.
C. Schulze, T. Weiske and H. Schwarz, Chimia 40 (1986) 362.
a) C. Schulze and H. Schwarz, Chi mi a 41 (1987) 202. (b) C. Schulze and H. Schwarz, J. Am. Chem. Soc. 110 (1988) 67. (c) C. Schulze, T. Weiske and H. Schwarz, Organometa11ics 7 (1988) 898. (d) C. Schulze and H, Schwarz, Chi mi a, in press.
S. Patai (Ed.): The Chemistry of Functional Groups: The Chemistry of Ketenes, Allenes and Related Compounds, Wiley. London (1980).
(a) N. Steinrück and H. Schwarz, Chimia 42 (1988) 000, (b) N. Steinrück and H. Schwarz, OrganometaIli cs, submitted.
(a) C. Wentrup: Reactive Molecules: The Neutral Reactive Intermediate in Organic Chemistry, Wiley, New York (1984). (b) W. W. Duley and D. A. Williams: Interstellar Chemistry, Academic Press, London (1984). (c) G. Winnewisser and E. Herbst, Top. Curr. Chem. 139 (1987) 119.
a) C. Wesdemiotis and F. W. McLafferty, Chem. Rev. 87 (1987) 485. (b) J. K. Terlouw arid H. Schwarz, Angew. Chem. Irrt, Ed. Engl. 26 (1987) 805. (c) J. L. Holmes, Acc. Chem. Res., submitted.
B. E. Koe I, B. E. Bent and G. A. Somorjai, Surf. Sci. 146 (1984) 211.
C. B. Lebrilla, T. Drewello and H. Schwarz, Organometallics 6 (1987) 2268.
J. Müller and P. Göser, J. Organomet. Chem. 12 (1968) 163.
J. Müller, Angew. Chem. Int. Ed. Engl. 11 (1972) 653.
T. Drewello and H. Schwarz, in preparation.
J. Müller and L. D’Or, J. Organomet. Chem. 10 (1967) 313.
K. Eller, D. Sülzle and H. Schwarz, Angew. Chem., submitted.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1989 Springer-Verlag Berlin Heidelberg
About this paper
Cite this paper
Czekay, G. et al. (1989). Remote Functionalization of Carbon-Hydrogen and Carbon-Carbon Bonds by Bare Transition Metal Ions in the Gas Phase. In: Werner, H., Erker, G. (eds) Organometallics in Organic Synthesis 2. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-74269-9_12
Download citation
DOI: https://doi.org/10.1007/978-3-642-74269-9_12
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-50531-0
Online ISBN: 978-3-642-74269-9
eBook Packages: Springer Book Archive