Zirconium-mediated conversion of amides to nitriles: A surprising additive effect

Angewandte Chemie - International Edition

Volumn 43, Issue 40, 2004, Pages 5375-5377

  Ruck, Rebecca T ^a   Bergman, Robert G ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Additive effects; Amides; Kinetics; Nitriles; Zirconium

Indexed keywords

CHLORINE COMPOUNDS; MOLECULAR DYNAMICS; NITRILE RESINS; PHASE TRANSITIONS; ZIRCONIUM;

AMIDES; INTRAMOLECULAR REACTIONS;

NITROGEN COMPOUNDS;

AMIDE; AMINE; DIMETHYLZIRCONOCENE; KETONE DERIVATIVE; NITRILE; NITROGEN; OXYGEN; UNCLASSIFIED DRUG; ZIRCONIUM; ZIRCONIUM DERIVATIVE; ZIRCONOCENE;

ARTICLE; CATALYSIS; CHEMICAL BOND; CHEMICAL MODIFICATION; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; CYCLOADDITION; DECOMPOSITION; ELIMINATION REACTION; HEATING; ISOTOPE LABELING; NITROGEN NUCLEAR MAGNETIC RESONANCE; PARAMETER; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; REPRODUCIBILITY; SYNTHESIS; TECHNIQUE; TEMPERATURE DEPENDENCE; X RAY DIFFRACTION;

AMIDES; MODELS, CHEMICAL; NITRILES; SOLUBILITY; SOLVENTS; ZIRCONIUM;

EID: 7244229660     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200461064     Document Type: Article

References (16)

1. S. R. Sandler, W. Karo in Organic Functional Group Preparations, Academic Press, San Diego, 1983, chap. 17.
2. D. B. Reisner, E. C. Coring, Org. Synth. Coll. Vol. IV 1963, 144.
3. J. A. Krynitsy, H. W. Carhart, Org. Synth. Coll. Vol. IV 1963, 436.
4. W. Lehnen, Tetrahedron Lett. 1971, 1501.
5. R. T. Ruck, R. G. Bergman, Organometallics 2004, 23, 2231.
6. R. Kupfer, S. Meier, E.-U. Würthwein, Synthesis 1984, 688.
7. 2] in toluene at 135 °C.
8. P. J. Walsh, F. J. Hollander, R. G. Bergman, Organometallics 1993, 12, 3705.
9. 2]: S. Couturier, B. Gautheron, J. Organomet. Chem. 1978, 757, C61.
10. -) were screened as additives.
11. 15N NMR spectrum.
12. 4NCl.
13. The reaction used in KIE studies is shown in Equation (2). The reaction rate was shown to be independent of [alkyne] under the conditions employed. diagram presented
14. Hydrogen bonding to the NH proton was ruled out as a possible mechanism because chloride can be used to accelerate the following reaction [Eq. (3)]. diagram presented
15. R. T. Ruck, R. L. Zuckerman, S. W. Krska, R. G. Bergman, Angew. Chem. 2004, 116; Angew. Chem. Int. Ed. 2004, 43
16. R. T. Ruck, R. L. Zuckerman, S. W. Krska, R. G. Bergman, Angew. Chem. 2004, 116; Angew. Chem. Int. Ed. 2004, 43