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Solid-phase organik syntheses - Burdges K.

Burdges K. Solid-phase organik syntheses - John Wiley & Sons, 2000. - 283 p.
ISBN 0-471-22824-9
Download (direct link): phaseorganicsynthesis2000.pdf
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Wavelength (nm)
Wavenumber (cm'"*) b
Figure 7.11. UV-Visible absorption of 9-anthroylnitrile in the supernatant (A) and single-bead FTIR spectra taken from the resin (B) before and after a 20-min reaction.
aldehydes and ketones has been developed.9 Hydroxyl groups are routinely quantitated by reaction with 9-anthroylnitrile for 20 min in DMF14; Figure 7.11 shows the UV-visible spectra of 9-anthroylnitrile in the supernatant and the single-bead IR spectra of the solid sample before and after a 20-min reaction. Similarly, carboxyl groups are routinely quantitated by reaction with 1-pyrenyldiazomethane for 50 min in ethyl acetate. In general, these methods take about 1 h or less and require 2-10-mg resin samples.
Cleave-and-analyze methods can be used in solid-phase organic syntheses, but direct spectroscopic analyses are convenient and sometimes provide
information that would be hard to obtain in any other way. The IR spectral shifts and peak-area changes can be used to observe intermediates in solid-phase syntheses. Single-bead FTIR spectroscopy, for instance, is a simple, sensitive, fast, and convenient method for following reactions on a solid support without stopping them or cleaving product from the resin. Single-bead FTIR can also provide kinetic information. Fourier transform FTIR internal reflection spectroscopy in the micro- and macro-formats is now the primary analytical method for monitoring of reactions directly on surface-functionalized polymers.
Dye-coupling/consumption techniques enable quantitation of functional groups on resin. However, this area is at an early stage of refinement; more quantitative analytical methods for quantifying a diverse set of organic functional groups are required.
The author is very grateful to co-workers at Novartis for participating in the projects described and to the co-authors in references 3a, 3b, 4c, 9, lOa-c, and 11-14. In particular, the author thanks Lina Liu, Robert Dunn, Qing Tang, Qun Sun, Wenbao Li, and Roger E. Marti for their contributions.
1. (a) Fridkin, .; Patchornik, A.; Katchalski, E. Use of Polymers as Chemical Reagents, J. Am. Chem. Soc. 1966, 88, 3164. (b) Leznoff, . C. The Use of Insoluble Polymer Supports in Organic Chemical Synthesis, Chem. Soc. Rev. 1974, 3, 65. (c) Crowley, J. I.; Rapoport, H. Solid-Phase Organic Synthesis Novelty or Fundamental Concept? Acc. Chem Res. 1976,9, 135. (d) Leznoff,
. C. The Use of Insoluble Polymer Supports in General Organic Synthesis, Acc. Chem Res. 1978, 77, 327. (e) Frechet, J. M. J. Synthesis and Applications of Organic Polymers as Supports and Protecting Groups, Tetrahedron 1981, 57, 663. (f) Hodge, P. Organic Reactions Using Polymer-Supported Catalysts, Reagents or Substrates, in Synthesis and Separations Using Functional Polymers, Sherrington, D. C., Hodge, P., Eds.; Wiley: New York, 1988, Chapter 2. (g) Fruchtel, J. S.; Jung, G. Organic Chemistry on Solid Supports, Angew Chem. Int. Ed. Engl. 1996, 35. (h) James, I. W. Recent Publications in Solid-Phase Chemistry: Part I, Mol. Diversity 1996,2, 175. (i) Hermkens, P. H. H., Ottenheijm, H. C. J.; Rees, D. Solid-Phase Organic Reactions: A Review of the Recent Literature, Tetrahedron 1996, 52,4527. (j) Brown, R.
Recent Developments in Solid-Phase Organic Synthsis, Contemp. Org. Syn. 1997, 4, 216.
2. (a) Furka, A.; Sebestyen, F.; Asgedom, .; Dibo, G. General Method for Rapid Synthesis of Multicomponent Peptide Mixtures, Int. J. Pept. Protein Res. 1991, 37,487. (b) Houghten, R. A.; Pinilla, C.; Blondelle, S. E.; Appel, J. R.; Dooley, . .; Cuervo, J. H. Generation and Use of Synthetic Peptide Combinatorial Libraries for Basic Research and Drug Discovery, Nature 1991, 354, 84. (c) Lam, K. S.; Salmon, S. E.; Hersh, E. .; Hruby, V. J.; Kazmierski, W. .; Knapp, R. J. A New Type of Synthetic Peptide Library for Identifying Ligand-Binding Activity, Nature 1991, 354, 82.
3. (a) Yan, B.; Kumaravel, G.; Anjaria, H.; Wu, A.; Petter, R.; Jewell, C. F., Jr.; Wareing, J. R. Infrared Spectrum of a Single Resin Bead for Real-Time Monitoring of Solid-Phase Reactions, J. Org. Chem. 1995,60,5736. (b) Yan,
B.; Kumaravel, G., Probing Solid-Phase Reactions by Monitoring the IR Bands of Compounds on a Single Flattened Resin Bead, Tetrahedron 1996, 52, 843. (c) Pivonka, D. E.; Russell, K.; Gero, T. Tools for Combinatorial Chemistry: In Situ Infrared Analysis of Solid-Phase Organic Reactions, Appl. Spectr. 1996, 50, 1471. (d) Pivonka, D. E.; Simpson, T. R. Tools for Combinatorial Chemistry: Real-Time Single-Bead Infrared Analysis of a Resin-Bound Photocleavage Reaction, Anal. Chem. 1997, 69, 3851.
4. (a) Hochlowski, J.; Sowin, .; Pan, J. Applications of Raman Spectroscopy to Combinatorial Chemistry, in Cyprus 98, New Technologies and Frontiers in Drug Research; 1998. (b) Rahman, S. S.; Busby, D. J.; Lee, D. C. Infrared and Raman Spectra of a Single Resin Bead for Analysis of Solid-Phase Reactions and Use in Encoding Combinatorial Libraries, J. Org. Chem. 1998,63,6196. (c) Yan, B.; Gremlich, H.-U.; Moss, S.; Coppola, G. .; Sun, Q.; Liu, L. A Comparison of Various FTIR and FT Raman Methods: Applications in the Reaction Optimization Stage of Combinatorial Chemistry, J. Comb. Chem. 1999, 1, 46.
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