Xiang-Ping Hu et al.
FULL PAPERS
red at room temperature for one hour under an argon atmos-
phere. To this Pd catalyst was added allylic pivalate 11a
(0.50 mmol) in CH2Cl2 (1.5 mL), followed by dimethyl malo-
nate (12a; 170 mL, 1.5 mmol), N,O-bis(trimethylsilyl)-acet-
amide (BSA, 0.37 mL, 1.5 mmol), and a catalytic amount of
KOAc sequentially. After stirring for 12 hours, the reaction
mixture was quenched with saturated aqueous NH4Cl solution
and diluted with CH2Cl2. The organic layer was separated,
dried over MgSO4, and concentrated under reduced pressure.
The residue was purified by column chromatography (hex-
ane:ethyl acetate, 8:1) to afford a pure product 13a. The enan-
tiomeric excess was determined by HPLC (Chiralpak AD, hex-
anes:2-propanol¼90:10, 1.0 mL/min). The absolute configu-
ration was determined by comparison of the specific rotation
with the literature value.[14]
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General Procedure for Asymmetric Allylic Amination
[7] X. Hu, H. Dai, C. Bai, H. Chen, Z. Zheng, Tetrahedron:
Asymmetry 2004, 15, 1065.
A solution of [Pd(h3-C3H5)Cl]2 (3.7 mg, 0.01 mmol) and chiral
ligand (0.03 mmol) in toluene (1.5 mL) was stirred at indicated
temperature for one hour under an argon atmosphere. To this
Pd catalyst was added allylic pivalate 11a (0.50 mmol) in tol-
uene (1.5 mL), followed by benzylamine (1.5 mmol). After
stirring for 24 hours, the reaction mixture was quenched with
saturated aqueous NH4Cl solution and diluted with CH2Cl2.
The organic layer was separated, dried over MgSO4, and con-
centrated under reduced pressure. The residue was purified
by column chromatography (hexane:ethyl acetate, 20:1) to af-
ford a pure product 14. The enantiomeric excess was deter-
mined by HPLC (Chiralcel OD, hexanes:2-propanol¼200:1,
0.6 mL/min).
[8] a) T. Hayashi, C. Hayashi, Y. Uozumi, Tetrahedron:
Asymmetry 1995, 6, 2503; b) X. Hu, H. Dai, X. Hu, H.
Chen, J. Wang, C. Bai, Z. Zheng, Tetrahedron: Asymme-
try 2002, 13, 1687; c) X. Hu, H. Chen, X. Hu, H. Dai, C.
Bai, J. Wang, Z. Zheng, Tetrahedron Lett. 2002, 43, 9179;
d) T. Tu, Y.-G. Zhou, X.-L. Hou, L.-X. Dai, X.-C. Dong,
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[9] a) N. W. Boaz, S. D. Debenham, E. B. Mackenzie, S. E.
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H. C. Dai, X. Q. Hu, Z. Zheng, Chin. Chem. Lett. 2003,
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Acknowledgements
[10] a) T. Hayashi, T. Mise, M. Fukushima, M. Kagotani, N.
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M. Konishi, K. Yamamoto, M. Kumada, Bull. Chem.
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We thank the National Natural Science Foundation of China for
financial support of this work (20472083).
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Adv. Synth. Catal. 2005, 347, 541–548