F. L. Lam et al. / Tetrahedron: Asymmetry 17 (2006) 497–499
499
Table 3. The results of Pd-catalyzed asymmetric allylic amination
3. Guiry, P. J.; Saunders, C. P. Adv. Synth. Catal. 2004, 346,
a
using (S,R
p
)-FerroNPS 2 as chiral ligand
497–537.
4
. (a) Selvakumar, K.; Valentini, M.; Worle, M.; Pregosin, P.
S.; Albinati, A. Organometallics 1999, 18, 1207–1215; (b)
Pretot, R.; Pfaltz, A. Angew. Chem., Int. Ed. 1998, 37,
OAc
NHBn
[
η3-C H PdCl] , 2
3
5
2
*
2
BnNH , EA, r.t.
Ph
Ph
Ph
Ph
3
23–325.
5. Gilbertson, S. R.; Lan, P. Org. Lett. 2001, 3, 2237–2240.
. (a) Albinati, A.; Pregosin, P. S.; Wick, K. Organometallics
996, 15, 2419–2421; (b) Selvakumar, K.; Valentini, M.;
Pregosin, P. S.; Albinati, A. Organometallics 1999, 18,
591–4597.
b
c
Entry Ligand Concn (M) Time (h) Yield (%)
ee (%)
6
1
2
3
2a
2b
2c
0.25
3.5
48
75
98
86
92
89.1 (S)
91.5 (S)
81.7 (S)
1
0.1 (THF)
0.1
4
a
3
Reaction conditions: [Pd(g -C
4.2 mol %), benzylamine (3.0 equiv), and EA as solvent at room
3
H
5
)Cl]
2
(2 mol %), ligand
2
7. (a) Evans, D. A.; Campos, K. R.; Tedrow, J. S.; Michael,
F. E.; Gagne, M. R. J. Org. Chem. 1999, 64, 2994–2995;
(b) Evans, D. A.; Campos, K. R.; Tedrow, J. S.; Michael,
F. E.; Gagne, M. R. J. Am. Chem. Soc. 2000, 122, 7905–
7920.
(
temperature.
Isolated yield.
b
c
The % ee value was determined by HPLC on an OJ-H column
0.4 mL/min, n-Hex/ PrOH = 85:15).
i
(
8. Mancheno, O. G.; Priego, J.; Cabrera, S.; Arrayas, R. G.;
Llamas, T.; Carretero, J. C. J. Org. Chem. 2003, 68, 3679–
3
686.
and amination, and excellent enantioselectivities and
chemical yields were observed. Further investigation of
other catalytic asymmetric reactions with these ferro-
cenyl N-P/S ligands is currently underway.
9
. Cabreba, S.; Arrayas, R. G.; Carretero, J. C. Angew.
Chem., Int. Ed. 2004, 43, 3944–3947.
0. Mancheno, O. G.; Arrayas, R. G.; Carretero, J. C. J. Am.
Chem. Soc. 2004, 126, 456–457.
1. Cabreba, S.; Arrayas, R. G.; Carretero, J. C. J. Am. Chem.
Soc. 2005, 127, 16394–16395.
2. Cabreba, S.; Arrayas, R. G.; Alonso, I.; Carretero, J. C.
J. Am. Chem. Soc. 2005, 127, 17938.
3. (a) Colacot, T. J. Chem. Rev. 2003, 103, 3101–3118; (b)
Dai, L.; Tu, T.; You, S.; Deng, W.; Hou, X. Acc. Chem.
Res. 2003, 36, 659–667.
4. Jia, X.; Li, X.; Lam, W. S.; Kok, Stanton H. L.; Xu, L.;
Lu, G.; Yeung, C. H.; Chan, Albert S. C. Tetrahedron:
Asymmetry 2004, 15, 2273–2278.
1
1
1
1
Acknowledgments
We thank the UGC Areas of Excellence Scheme (AoE/
P-10/01) and The Hong Kong Polytechnic University
(
ASD) for financial support.
1
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