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For some racemic approaches to yohimbane, see: (a) Wender, P. A.; Smith, T. E. J. Org. Chem. 1996, 61, 824. (b) Naito, T.; Miyata, O.; Tada, Y.; Nishiguchi, Y.; Kiguchi, T.; Ninomiya, I. Chem. Pharm. Bull. 1986, 34, 4144. Martin, S. F.; Williamson, S. A.; Gist, R. P.; Smith, K. M. J. Org. Chem. 1983, 48, 5170. (e) Kametani, T.; Suzuki, T.; Unno, K. Tetrahedron 1981, 37, 3819. (f) Rosenmund, P.; Trommer, W.; Dorn-Zachertz, D.; Ewerdwalbesloh, U. Liebigs Ann. Chem. 1979, 1643. (g) Morrison, G. C.; Cetenko, W. A.; Shavel, J., Jr. J. Org. Chem. 1966, 31, 2695. These workers prepared (-)-yohimbane by resolution of racemic yohimbane. (e) van Tamelen, E. E.; Shamma, M.; Aldrich, P. J. Am. Chem. Soc. 1956, 78, 4628. (f) Corsano, S.; Panizzi, L. Ann. Chim. 1958, 48, 1025.
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2 was added to the reaction at 0 °C and the reaction then allowed to warm to room temperature and stirred for 24 h, the ratio of 20b:20b was observed to be ca. 2:1.
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10 we assigned the stereochemistry of a mixture of 20a and 20b using NOE and NOESY spectroscopy. Since then, we have developed an HPLC method for the baseline separation of these diastereomers on an analytical scale. Unfortunately, all of our attempts to separate these diastereomers on a preparative scale were not successful, as we could load only less than 1 mg of sample and still not obtain separation that was seen on an analytical scale.
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2 prior to use. Exact mass measurements recorded in the electron impact (EI) or fast atom bombardment (FAB) modes were determined at The Ohio State University Campus Chemical Instrument Center with a Kratos MS-30 mass spectrometer. Combustion analyses were performed at Quantitative Technologies Inc., Whitehouse, NJ. Optical rotations were recorded using a Perkin-Elmer 241 model polarimeter.
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