Palladium-Catalyzed Oxidative Kinetic Resolution with Ambient Air as the Stoichiometric Oxidation Gas

Angewandte Chemie - International Edition

Volumn 43, Issue 3, 2004, Pages 353-357

  Bagdanoff, Jeffrey T ^a   Stoltz, Brian M ^a  

^a California Institute of Technology   (United States)

Author keywords

Asymmetric catalysis; Hydrogen bonds; Oxidation; Oxygen; Palladium; Solvent effects

Indexed keywords

AIR; ALCOHOLS; CATALYSIS; HYDROGEN BONDS; PALLADIUM; REACTION KINETICS; STOICHIOMETRY;

KINETIC RESOLUTION;

OXIDATION;

ALCOHOL; HALIDE; PALLADIUM; SPARTEINE;

AMBIENT AIR; ARTICLE; CATALYSIS; CHEMICAL REACTION KINETICS; ENANTIOSELECTIVITY; HYDROGEN BOND; OXIDATION; ROOM TEMPERATURE; SOLVATION; STOICHIOMETRY;

AIR; ALCOHOLS; CATALYSIS; HYDROGEN BONDING; KINETICS; OXIDATION-REDUCTION; OXYGEN; PALLADIUM; SOLVENTS; STEREOISOMERISM;

EID: 0346500606     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200352444     Document Type: Article

References (23)

1. a) E. M. Ferreira, B. M. Stoltz, J. Am. Chem. Soc. 2001, 123, 7725;
2. b) J. T. Bagdanoff, E. M. Ferreira, B. M. Stoltz, Org. Lett. 2003, 5, 835.
3. Simultaneous to our publication of reference [1a], a related system was reported: D. R. Jensen, J. S. Pugsley, M. S. Sigman, J. Am. Chem. Soc. 2001, 123, 7475.
4. 2: T. Nishimura, K. Ohe, S. Uemura, J. Org. Chem. 1999, 64, 6750.
5. For examples of related enzymatic oxidative kinetic resolutions, see: a) K. Faber, Biotransformations in Organic Chemistry, 3rd ed., Springer, Berlin, 1997, pp. 201-205;
6. b) I. J. Jackovac, H. B. Goodbrand, K. P. Lok, J. B. Jones, J. Am. Chem. Soc. 1982, 104, 4659-4665.
7. Recently, mechanistic details of related non-asymmetric systems were studied: a) B. A. Steinhoff, S. S. Stahl, Org. Lett. 2002, 4, 4179;
8. b) B. A. Steinhoff, S. S. Stahl, J. Am. Chem. Soc. 2002, 124, 766;
9. c) S. S. Stahl, J. L. Thorman, R. C. Nelson, M. A. Kozee, J. Am. Chem. Soc. 2001, 123, 7188.
10. For discussions on kinetic resolution, see: a) V. S. Martin, S. S. Woodard, T. Katsuki, Y. Yamada, M. Ikeda, K. B. Sharpless, J. Am. Chem. Soc. 1981, 103, 6237;
11. b) C.-S. Chen, Y. Fujimoto, G. Girdaukas, C. J. Sih, J. Am. Chem. Soc. 1982, 104, 7294;
12. c) H. B. Kagan, J. C. Fiaud in Topics in Stereochemistry, Vol. 18 (Ed.: E. L. Eliel), Wiley, New York, 1988, pp. 249-330.
13. 2 is equally soluble. For relevant tables, see: F. Fischer, G. Pfleiderer, Z. Anorg. Allg. Chem. 1922, 124, 61;
14. b) No correlation between solvent dielectric constant (an estimate of polarity) and conversion is apparent; for relevant tables, see: E. W. Flick in Industrial Solvents Handbook, 3rd ed. (Ed.: E. W. Flick), Noyes Data Corp., New Jersey, 1985, pp. 637-647.
15. a) No dichlorocarbene was detected under the reaction conditions;
16. 3] complex (see Supporting Information for the solid-state structure). This complex is inactive as a catalyst for kinetic resolution under a variety of conditions.
17. rel(fast/slow) = ln[(1 - C)(1 - ee)]/ln[(1 - C)(1 + ee)] (C = conversion).
18. For an example of a non-asymmetric oxidation of alcohols catalyzed by palladium in the presence of air as the stoichiometric oxidant, see: K. Hallman, C. Moberg, Adv. Synth. Catal. 2001, 343, 260.
19. 2) gives identical results. Chloroform stabilized by EtOH must be distilled prior to use.
20. 3 is not involved as an oxidant.
21. We recently reported a number of palladium-catalyzed oxidative hetero- and carbocyclization reactions with molecular oxygen: a) R. M. Trend, Y. K. Ramtohul, E. M. Ferreira, B. M. Stoltz, Angew. Chem. 2003, 115, 2998-3001; Angew. Chem. Int. Ed. 2003, 42, 2892-2895;
22. We recently reported a number of palladium-catalyzed oxidative hetero- and carbocyclization reactions with molecular oxygen: a) R. M. Trend, Y. K. Ramtohul, E. M. Ferreira, B. M. Stoltz, Angew. Chem. 2003, 115, 2998-3001; Angew. Chem. Int. Ed. 2003, 42, 2892-2895;
23. b) E. M. Ferreira, B. M. Stoltz, J. Am. Chem. Soc. 2003, 125, 9578-9579.