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General Procedures (a) Racemic catalysts: A Schlenk flask was charged with the educt (typically 0.060-0.080 g, Then C6H 5Cl or C6H6 solutions that were 0.0125 M in ClCH2CH2Cl (reference for 1H NMR integration) were added to give 0.100 M educt solutions. These were equilibrated to 20°C using a cryostat. Solutions of C6H5Cl or C 6H6 that were 0.0100 M in catalyst and 0.0125 M in ClCH2CH2Cl were cooled to 0°C. Equal corresponding to 10 mol% loading, were added dropwise over ca. 5 min to the educt solutions. An aliquot (0.6 mL) was transferred to an NMR tube, and 1H NMR spectra were periodically recorded. When the reaction was complete (or no further reaction took place, 5 of hexane were added with stirring. The mixture was filtered through a short plug of silica gel removing catalyst, and the plug was
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5Cl were further purified by silica gel column chromatography, except in the case of 5a.
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24
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34247160650
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Enantiopure catalysts: The preceding reactions were repeated on 0.0010-0.0020 g scales. The products were analyzed by HPLC using Chiralcel OD, Chiralpak AD-H or Chiralpak AS-H columns.
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(b) Enantiopure catalysts: The preceding reactions were repeated on 0.0010-0.0020 g scales. The products were analyzed by HPLC using Chiralcel OD, Chiralpak AD-H or Chiralpak AS-H columns.
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25
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34247105145
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All products were characterized by NMR (1H, 13C) and IR spectroscopy, and these data are available from the authors upon request; 3a,d and 5a have been reported previously.11a,15,16 Typical data (3b, 1H NMR (400 MHz, CDCl3, δ, 1.39 [d, CH3)2CH, 3J(H,H, 7.2 Hz, 6 H, 1.82-1.91 (m, C=CHCHH′, 1 H, 2.27-246 (2 m, C=CHCHH′, CHH′CHOH, 2 H) 2.62-2.73 (m, CHH′CHOH, 1 H, 2.78 (br s, CHOH, 1 H, 3.74 [sep, 3J(H,H, 7.2 Hz, CH3)2CH, 1 H, 5.13-5.16 (m, CHOH, 1 H, 6.89 [dd, 3J(H,H, 2.8, 2.8 Hz, C=CHCHH′, 1 H] ppm. 13C{1H} NMR (101 MHz, CDCl3, δ, 23.0 [s, CH3) 2CH, 30.9 (s, C=CHCH2, 31.8 s, CH 2CHOH, 34.3 [s, CH
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