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Recently, Jørgensen and co-workers reported L-proline-catalyzed direct asymmetric α-aminations of alkyl methyl ketones with azodicarboxylates, which led to a mixture of the expected 3-hydrazino ketones (up to 99% ee) and 1-hydrazino regioisomers (76:24-91:9 regioselectivity): Kumaragurubaran, N.; Juhl, K.; Zhuang, W.; Bøgevig, A.; Jørgensen, K. A. J. Am. Chem. Soc. 2002, 124, 6254-6255.
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(a) Recently, Jørgensen and co-workers reported L-proline-catalyzed direct asymmetric α-aminations of alkyl methyl ketones with azodicarboxylates, which led to a mixture of the expected 3-hydrazino ketones (up to 99% ee) and 1-hydrazino regioisomers (76:24-91:9 regioselectivity): Kumaragurubaran, N.; Juhl, K.; Zhuang, W.; Bøgevig, A.; Jørgensen, K. A. J. Am. Chem. Soc. 2002, 124, 6254-6255.
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For reviews on transition-metal-catalyzed enantioselective aziridination of alkenes with (arylsulfonylimino)phenyliodinanes and arylsulfonyl azides, see: a, Jacobsen, E. N, Pfaltz, A, Yamamoto, H, Eds, Springer: Berlin, Chapter 17, pp
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For reviews on transition-metal-catalyzed enantioselective aziridination of alkenes with (arylsulfonylimino)phenyliodinanes and arylsulfonyl azides, see: (a) Jacobsen, E. N. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Vol. 2, Chapter 17, pp 607-618.
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For enantioselective amination of silyl enol ethers using stoichiometric amounts of chiral nitridomanganese complexes, see: (a) Minakata, S.; Ando, T.; Nishimura, M.; Ryu, I.; Komatsu, M. Angew. Chem., Int. Ed. 1998, 37, 3392-3394.
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4, as a catalyst; see: Reddy, R. P.; Davies, H. M. L. Org. Lett. 2006, 8, 5013-5016.
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4, as a catalyst; see: Reddy, R. P.; Davies, H. M. L. Org. Lett. 2006, 8, 5013-5016.
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26
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35948935367
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For the determination of absolute stereochemistry, see the Supporting Information
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For the determination of absolute stereochemistry, see the Supporting Information.
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27
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35948964522
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A survey of solvents revealed that CH2Cl2 was the optimal solvent for this transformation
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3, 6 h, 95% yield, 85% ee).
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3, 6 h, 95% yield, 85% ee)
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34
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35948936902
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No reaction was observed when the (E)-isomer of 3f (Z/E = 1:>99) was used.
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No reaction was observed when the (E)-isomer of 3f (Z/E = 1:>99) was used.
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