Facile metal-assisted hydrolysis of a urethane

Organic Letters

Volumn 3, Issue 24, 2001, Pages 3895-3898

  Kelly, T Ross ^a   Cavero, Marta ^a   Zhao, Yajun ^a  

^a BOSTON COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

METAL; URETHAN;

ARTICLE; CHEMISTRY; HYDROLYSIS; KINETICS;

HYDROLYSIS; KINETICS; METALS; SUPPORT, U.S. GOV'T, P.H.S.; URETHANE;

EID: 0035969614     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol016867z     Document Type: Article

References (22)

1. (a) Kelly, T. R.; de Silva, H.; Silva, R. A. Nature 1999, 400, 150.
2. (b) Kelly, T. R.; Silva, R. A.; de Silva, H.; Jasmin, S.; Zhao, Y. J. Am. Chem. Soc. 2000, 122, 6935.
3. (c) Kelly, T. R. Acc. Chem. Res. 2001, 34, 514.
4. (a) Hegarty, A. F. In Derivatives of Carbon Dioxide, Comprehensive Organic Chemistry; Barton, D. H. R., Ollis, W. D. Eds.; Pergamon Press: Oxford, 1979; Vol. 2, p 1067.
5. (b) Heywang, G.; Petersen, U. In Kohlensaure-Derivative, Methoden der Organischen Chemie (Houben-Weyl); Georg Thieme Verlag: Stuttgart, 1983; Vol. E4, p 1.
6. (c) Adams, P.; Baron, F. A. Chem. Rev. 1965, 65, 567.
7. Brown, R. S.; Bennet, A. J.; Slebocka-Tilk, H. Acc. Chem. Res. 1992, 25, 481.
8. Dittert, K. W.; Higuchi, T. J. Pharm. Sci. 1963, 52, 852.
9. Groves, J. T.; Baron, L. A. J. Am. Chem. Soc. 1989, 111, 5442.
10. For instance, see reviews: (a) Reichwein, A. M.; Verboom, W.; Reinhoudt, D. N. Rec. Trav. Chim. Pays-Bas 1994, 113, 343.
11. (b) Chin, J. Acc. Chem. Res. 1991, 24, 145 and references therein.
12. See Supporting Information for experimental details and spectral characterization.
13. For additional details on procedures employed during kinetic studies, see Supporting Information.
14. 1H NMR was precluded due to the paramagnetism of Cu(II).
15. The competitive mechanism known for carbamate hydrolysis via formation of an isocyanate intermediate by initial loss of the nitrogen proton could be ruled out in this system since the proton has been substituted by a methyl group. See ref 4.
16. Zuman, P.; Patel, R. C. Techniques in Organic Reaction Kinetics; John Wiley & Sons: New York, 1984; pp 145-192.
17. Determination of the ionization constants was performed using the minimum amount of organic solvent possible in order to avoid damage to the electrode.
18. Suh, J.; Son, S. J.; Myunghyun, P. S. Inorg. Chem. 1998, 37, 4872.
19. Albert, A.; Serjeant, E. P. The Determination of Ionization Constants; Chapman and Hall: London, 1984; 3rd ed., p 31 and references therein.
20. obs values for higher pHs instead of the observed leveling off (Figure 2; see also ref 11 and Breslow, R.; Schepartz, A. J. J. Am. Chem. Soc. 1987, 109, 1814). On the other hand, intramolecular attack of metal-bound water/hydroxide onto the coordinated carbonyl would be disfavored on the basis of geometric constraints.
21. For similar complexes and a detailed description of their structure, see, for example: Young, M. J.; Wahnon, D.; Hynes, R. C.; Chin, J. J. Am. Chem. Soc. 1995, 117, 9441.
22. Menger has proposed an "optimal" distance for intramolecular carbonyl addition to be a value close to 2.8 Å: Menger, F. M. Acc. Chem. Res. 1985, 18, 128.