1692
X. Hu et al. / Tetrahedron: Asymmetry 13 (2002) 1687–1693
15H); 31P NMR l −24.0. HRMS (FAB) calcd for
C32H29N2O2PFe+H 561.1393, found 561.1387.
3. (a) Kubota, H.; Koga, K. Tetrahedron Lett. 1994, 35,
6689–6692; (b) Wimmer, P.; Widhalm, M. Tetrahedron:
Asymmetry 1995, 6, 657–660; (c) Bourghida, M.; Wid-
halm, M. Tetrahedron: Asymmetry 1998, 9, 1073–1083;
(d) Widhalm, M.; Mereiter, K.; Bourghida, M. Tetra-
hedron: Asymmetry 1998, 9, 2983–2986; (e) Cahill, J. P.;
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4.3.11.
(R)-N-(3-Nitrobenzylidene)-1-[(S)-2-(diphenyl-
phosphino)ferrocenyl]phenylmethylamine, 6l. Yellow
solid; 51% yield; mp 152–154°C; [h]2D5 −450 (c 0.22,
CHCl3); H NMR (CCl4) l 3.91 (s, 1H), 3.96 (s, 5H),
1
4.37 (s, 1H), 4.47 (s, 1H), 5.88 (d, J=2.8 Hz, 1H),
6.95–8.14 (m, 20H); 31P NMR l −24.1. HRMS (FAB)
calcd for C36H29N2O2PFe+H 609.1393, found 609.1380.
4.4. General procedure for asymmetric allylic
alkylations
A solution of [Pd(h3-C3H5)Cl]2 (3.7 mg, 0.01 mmol)
and chiral phosphine–imine 6 (0.025 mmol) in toluene
(1.5 mL) was stirred at room temperature for 1 h under
argon. To this Pd-catalyst was added allylic acetate 7a
or pivalate 7b (0.50 mmol) in toluene (1.5 mL), fol-
lowed by dimethyl malonate (170 mL, 1.5 mmol), N,O-
bis(trimethylsilyl)-acetamide (BSA, 0.37 mL, 1.5 mmol),
and a catalytic amount of KOAc sequentially. After
stirring for 24 h, the reaction mixture was quenched
with a 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
(hexane:ethyl acetate, 8:1) to afford a pure product 8.
The enantiomeric excess was determined by HPLC
(Chiralpak AD, hexanes:2-propanol=90:10, 1.0 mL/
min). The absolute configuration was determined by the
specific rotation with a literature value.16
5. (a) Ito, K.; Kashiwagi, R.; Iwasaki, K.; Katsuki, T.
Synlett 1999, 1563–1566; (b) Han, J. W.; Jang, H.-Y.;
Chung, Y. K. Tetrahedron: Asymmetry 1999, 10, 2853–
2861; (c) Ito, K.; Kashiwagi, R.; Hayashi, S.; Uchida, T.;
Katsuki, T. Synlett 2001, 284–286.
6. Mino, T.; Shiotsuki, M.; Yamamoto, N.; Suenaga, T.;
Sakamoto, M.; Fujita, T.; Yamashita, M. J. Org. Chem.
2001, 66, 1795–1797.
Acknowledgements
7. (a) Saitoh, A.; Morimoto, T.; Achiwa, K. Tetrahedron:
Asymmetry 1997, 8, 3567–3570; (b) Saitoh, A.; Achiwa,
K.; Morimoto, T. Tetrahedron: Asymmetry 1998, 9, 741–
744; (c) Saitoh, A.; Achiwa, K.; Tanaka, K.; Morimoto,
T. J. Org. Chem. 2000, 65, 4227–4240.
The authors would like to thank the National Natural
Science Foundation of China for financial support of
this work (29933050).
8. (a) Jin, M.-J.; Jung, J.-A.; Kim, S.-H. Tetrahedron Lett.
1999, 40, 5197–5198; (b) Okuyama, Y.; Nakano, H.;
Hongo, H. Tetrahedron: Asymmetry 2000, 11, 1193–1198.
9. Mino, T.; Hata, S.; Ohtaka, K.; Sakamoto, M.; Fujita, T.
Tetrahedron Lett. 2001, 42, 4837–4839.
10. (a) Suzuki, Y.; Ogata, Y.; Hiroi, K. Tetrahedron: Asym-
metry 1999, 10, 1219–1222; (b) Jang, H.-Y.; Seo, H.;
Han, J. W.; Chung, Y. K. Tetrahedron Lett. 2000, 41,
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11. Kohara, T.; Hashimoto, Y.; Saigo, K. Synlett 2000,
517–519.
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13. Hayashi, T.; Hayashi, C.; Uozumi, Y. Tetrahedron:
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