Carboxylate-directed highly stereoselective homogeneous hydrogenation of cyclic olefins with Wilkinson's catalyst

Organic Letters

Volumn 5, Issue 9, 2003, Pages 1587-1589

  Zhang, Mingbao ^a   Zhu, Lei ^a   Ma, Xin ^a   Dai, Miao ^a   Lowe, Derek ^a  

^a BAYER CORPORATION   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; CARBOXYLIC ACID;

ARTICLE; CATALYST; EXPERIMENT; HYDROGENATION; REFORMATSKY REACTION; SAPONIFICATION; STEREOCHEMISTRY; X RAY ANALYSIS;

EID: 0141519198     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034464o     Document Type: Article

References (26)

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3. (b) Thompson, H. W.; McPherson, E. J. Am. Chem. Soc. 1974, 96, 6232.
4. For applications of the Thompson method in the synthesis of complex organic molecules, see: (c) McCombie, S. W.; Cox, B.; Lin, Sue-Ing; Ganguly, A. K.; McPhail, A. T. Tetrahedron Lett. 1990, 2083. (d) Callam, C. S.; Lowary, T. L. Org. Lett. 2000, 2, 167. (e) Preston, S. A.; Cupertino, D. C.; Palma-Ramirez, P.; Cole-Hamilton, D. J. J. Chem. Soc., Chem. Commun. 1986, 977.
5. For applications of the Thompson method in the synthesis of complex organic molecules, see: (c) McCombie, S. W.; Cox, B.; Lin, Sue-Ing; Ganguly, A. K.; McPhail, A. T. Tetrahedron Lett. 1990, 2083. (d) Callam, C. S.; Lowary, T. L. Org. Lett. 2000, 2, 167. (e) Preston, S. A.; Cupertino, D. C.; Palma-Ramirez, P.; Cole-Hamilton, D. J. J. Chem. Soc., Chem. Commun. 1986, 977.
6. For applications of the Thompson method in the synthesis of complex organic molecules, see: (c) McCombie, S. W.; Cox, B.; Lin, Sue-Ing; Ganguly, A. K.; McPhail, A. T. Tetrahedron Lett. 1990, 2083. (d) Callam, C. S.; Lowary, T. L. Org. Lett. 2000, 2, 167. (e) Preston, S. A.; Cupertino, D. C.; Palma-Ramirez, P.; Cole-Hamilton, D. J. J. Chem. Soc., Chem. Commun. 1986, 977.
7. Brown, J. M.; Chaloner, P. A.; Kent, A. G.; Murrer, B. A.; Nicholson, P. N.; Parker, D.; Sidebottom, P. J. J. Organomet. Chem. 1981, 216, 263.
8. (a) Crabtree, R. H.; Felkin, H.; Morris, G. E. J. Organomet. Chem. 1977, 141, 205.
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10. (c) Crabtree, R. H.; Demou, P. C.; Eden, D.; Mihelcic, J. M.; Parnell, C. A.; Quirk, J. M.; Morris, G. E. J. Am. Chem. Soc. 1982, 104, 6994.
11. (a) Stock, G.; Kahne, D. E. J. Am. Chem. Soc. 1983, 105, 1072.
12. (b) Schultz A.; McCloskey P. J. J. Org. Chem. 1985, 50, 5905.
13. (c) Brown, J. M.; Hall, S. A. Tetrahedron Lett. 1984, 25, 1393.
14. (d) Brown, J. M.; Naik, R. G. J. Chem. Soc., Chem. Commun. 1982, 348.
15. (e) Takagi, M.; Yamamoto, K. Tetrahedron 1991, 47, 8869.
16. Price from 2002-2003 Aldrich catalog: Wilkinson's catalyst, $70 000/mol; Crabtree's catalyst, $700 000/mol.
17. With Wilkinson's catalyst, displacement of the chloride ligand by the directing group is required for efficient stereoselective delivery of hydrogen. For more in-depth discussion on this point, see ref 1.
18. - 6.29. Data from: Pearson, R. G.; Sobel, H.; Songstad, J. J. Am. Chem. Soc. 1968, 90, 319.
19. Base-promoted coordination of the carboxyl to Rh via the carboxylate anion has been indicated to be responsible for enhancing enatioselectivity and catalyst turnovers in enatioselective hydrogenations catalyzed by rhodium complexes of chiral ligands. See: (a) Ojima, I.; Kogure, T.; Yoda, N. J. Org. Chem. 1980, 45, 4728. (b) Valentine, D., Jr.; Sun, R. C.; Toth, K. J. Org. Chem. 1980, 45, 3703.
20. Base-promoted coordination of the carboxyl to Rh via the carboxylate anion has been indicated to be responsible for enhancing enatioselectivity and catalyst turnovers in enatioselective hydrogenations catalyzed by rhodium complexes of chiral ligands. See: (a) Ojima, I.; Kogure, T.; Yoda, N. J. Org. Chem. 1980, 45, 4728. (b) Valentine, D., Jr.; Sun, R. C.; Toth, K. J. Org. Chem. 1980, 45, 3703.
21. (a) Shriner, R. L. Org. React. 1942, 1, 1.
22. (b) Rathke, M. W. Org. React. 1975, 22, 423.
23. Column, Chiracel AD, 4.6 (i.d.) x 250 mm; mobile phase A, 0.1% TFA (trifluoroacetic acid) in hexanes, mobile phase B, 0.1% TFA in IPA (isopropyl alcohol); method, isocratic 95% A (5%B), 20 min; flow rate, 1.5 mL/min; detector (UV), 284 nm. Retention times for the four diastereomers are 5.163 (SR), 6.255 (RS), 10.262 (RR), and 14.399 min (SS); the first letter denotes the absolute configuration of the carbon adjacent to the carboxyl group. The stereochemistry assignment for each peak is described as the following: a nonequal racemic diastereomeric mixture was analyzed by chiral HPLC to obtain 4 baseline-resolved peaks. Peaks 3 and 4, 1 and 2 are enantiomer pairs based on UV integration. The absolute configuration of peak 4 is determined to be SS by X-ray structural analysis. Peak 3 can then be assigned a RR configuration with certainty. The absolute configurations of peaks 1 and 2 were determined by another experiment. Optically active (S)-indene acid (96% ee) from the chemical resolution was subjected to diastereoselective hydrogenation. The indane acid obtained was then analyzed by chiral HPLC. Due to high diastereoselectivity of the hydrogenation (>99% de), only the (SR)-diastereomer peak should be detectable by HPLC (retention time 5.363 min, ca. 0.97% area) in addition to the desired SS diastereomer (major) and its enantiomer RR. The 2nd peak from the 1st experiment (6.255 min) can then be assigned an RS configuration with certainty.
24. The racemate of the indene substrate (1) can be resolved chemically with quinine prior to the stereoselective hydrogenation. The resolution yielded the (S)-enantiomer as the less soluble diastereomeric salt in acetonitrile (34%yield, 96-97% ee). The free acid was liberated by dissolving the salt in 2 N aqueous HCl followed by extraction into methylene chloride. The (SS)-enantiomer of 1a was then readily obtained in high ee after hydrogenation.
25. CRC Handbook of Chemistry and Physics; Weast, R., Ed.; The Chemical Rubber Co.: Cleveland, OH, 1969; p B-114.
26. 1H NMR integration. In both cases, the minor diastereomer was not detected.