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DMSO was purified by the distillation over CaH2 under reduced pressure after standing over CaH2 overnight: Armarego, W. L. F.; Chai, C. L. L. Purification of Laboratory Chemicals, 5th ed.; Elsevier: Burlington, 2003.
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DMSO was purified by the distillation over CaH2 under reduced pressure after standing over CaH2 overnight: Armarego, W. L. F.; Chai, C. L. L. Purification of Laboratory Chemicals, 5th ed.; Elsevier: Burlington, 2003.
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Typical Experimental Procedure (Table 1, To a DMSO solution (0.40 mL) or aq DMSO solution (DMSO: 0.40 mL; H2O: 22 μL) of amino acid (0.12 mmol) were added p- nitrobenzaldehyde (60.5 mg, 0.4 mmol) and cyclohexanone (207 μL, 2.0 mmol) under an argon atmosphere at r.t. When the reaction was complete, it was quenched with pH 7.0 phosphate buffer solution. The organic materials were extracted with EtOAc (3 x) and the combined organic extracts were dried over anhyd Na2SO4, and concentrated in vacuo after filtration. The residue was purified by flash chromatography to give an aldol product. Diastereoselectivity was determined by 1H NMR (400 MHz, Enantiomeric excess was determined by HPLC analysis with a Chiralpak AS-H column hexane-2-pro-panol, 10:1, λ, 231 nm, 1.0 mL/min; major enantiomer tR= 11.5 min, minor enantiomer tR, 18.7 min
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1H NMR (400 MHz). Enantiomeric excess was determined by HPLC analysis with a Chiralpak AS-H column (hexane-2-pro-panol = 10:1, λ = 231 nm), 1.0 mL/min; major enantiomer tR= 11.5 min, minor enantiomer tR = 18.7 min.
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All compounds are known
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All compounds are known:
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60
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2-(Hydroxy-4-nitrophenyl-methyl)cyclohexanone: Cobb, A. J. A.; Shaw, D. M.; Longbottom, D. A.; Gold, J. B.; Ley, S. V. Org. Biomol. Chem. 2005, 3, 84.
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(a) 2-(Hydroxy-4-nitrophenyl-methyl)cyclohexanone: Cobb, A. J. A.; Shaw, D. M.; Longbottom, D. A.; Gold, J. B.; Ley, S. V. Org. Biomol. Chem. 2005, 3, 84.
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61
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46649089200
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2-(2-Chlorophenylhydroxy-methyl)cyclohexanone: Chen, J.; Lu, H.; Li, X.; Cheng, L.; Wan, J.; Xiao, W. Org. Lett. 2003, 5, 4369.
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(b) 2-(2-Chlorophenylhydroxy-methyl)cyclohexanone: Chen, J.; Lu, H.; Li, X.; Cheng, L.; Wan, J.; Xiao, W. Org. Lett. 2003, 5, 4369.
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62
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34250371777
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4-Hydroxy-4-(4-nitrophenyl)-2-butanone: Rodriguez, B.; Bruckmann, A.; Bolm, C. Chem. Eur. J. 2007, 13, 4710.
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(c) 4-Hydroxy-4-(4-nitrophenyl)-2-butanone: Rodriguez, B.; Bruckmann, A.; Bolm, C. Chem. Eur. J. 2007, 13, 4710.
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63
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4-(2-Chlorophenyl)-4-hydroxy-2-butanone: Maya, V.; Raj, M.; Singh, V. K. Org. Lett. 2007, 9, 2593.
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(d) 4-(2-Chlorophenyl)-4-hydroxy-2-butanone: Maya, V.; Raj, M.; Singh, V. K. Org. Lett. 2007, 9, 2593.
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64
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33947252405
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l-(2-Chloro-phenyl)-l-hydroxy-3-pentanone and 4-(2-chlorophenyl)-4- hydroxy-3-methyl-2-butanone: Luo, S.; Xu, H.; Li, J.; Zhang, L.; Cheng, J.-P. J. Am. Chem. Soc. 2007, 129, 3074.
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(e) l-(2-Chloro-phenyl)-l-hydroxy-3-pentanone and 4-(2-chlorophenyl)-4- hydroxy-3-methyl-2-butanone: Luo, S.; Xu, H.; Li, J.; Zhang, L.; Cheng, J.-P. J. Am. Chem. Soc. 2007, 129, 3074.
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