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Pure Appl. Chem., 2008, Vol. 80, No. 5, pp. 1055-1062

http://dx.doi.org/10.1351/pac200880051055

Cu(I)-catalyzed asymmetric allylation of ketones and ketimines

Motomu Kanai, Reiko Wada, Tomoyuki Shibuguchi and Masakatsu Shibasaki

Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

References

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  • 9. CuF?3PPh3 is a stable, isolable, and well-defined CuF species. See: D. J. Gulliver, W. Levason, M. Webster. Inorg. Chim. Acta 52, 153 (1981). (http://dx.doi.org/10.1016/S0020-1693(00)88590-4)
  • 10. Direct spectroscopic observation of allylcopper was not possible.
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  • 12. This idea is supported by the fact that the linear product was the only observed isomer (46 % yield) in the Cu-catalyzed crotylation of a bulky ketone, t-butyl methyl ketone, using (E)- and (Z)-2.
  • 13. AgF-catalyzed allylation of aromatic aldehydes is significantly faster than that of aliphatic aldehydes. See: A. Yanagisawa, H. Kageyama, Y. Nakatsuka, K. Asakawa, Y. Matsumoto, H. Yamamoto. Angew. Chem., Int. Ed. 38, 3701 (1999). (http://dx.doi.org/10.1002/(SICI)1521-3773(19991216)38:24<3701::AID-ANIE3701>3.0.CO;2-D)
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  • 15. Consistent with this spectroscopic observation, LiOiPr did not catalyze the allylation reaction in the absence of Cu.
  • 16. Although no interaction between La(OiPr)3 and 1 was observed in 11B NMR, it is reasonable to assume that La(OiPr)3 accelerates the reaction by the same mechanism as LiOiPr.
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  • 19. Representative results of optimization [acetophenone-derived N-benyzyl ketimine was used as a substrate and CuOTf?0.5benzene (10 mol %)-iPr-DUPHOS (11 mol %) was used as a catalyst in toluene at 0 degC for 24 h]: 81 % ee, 75 % (+30 mol % of KOtBu); 10% ee, 91 % (+30 mol % of LiOiPr); 78 % ee, 94 % (+10 mol % of KOtBu and 20 mol % of LiOiPr).
  • 20. A representative procedure for CuOtBu-catalyzed asymmetric allylation of ketones: CuOTf?0.5benzene (4 mg, 0.016 mmol), (R,R)-iPr-DUPHOS (9 mg, 0.021 mmol), and KOtBu (5 mg, 0.048 mmol) were dissolved in DMF (0.18 mL), and the mixture was stirred at room temperature for 15 min. After cooling to -40 degC, allylboronate (121 mL, 0.64 mmol) and a ketone (0.533 mmol) were added successively. The reaction was monitored by TLC, and quenched with 10 % citric acid after the starting material was completely consumed.