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H. Nakano et al. / Tetrahedron Letters 43 (2002) 7761–7764
We have examined five new chiral xylofuranose-based
phosphinooxathiane and phosphinooxazinane ligands 1
and 2a–d. Particularly, 2d has been found to be an
efficient ligand for the asymmetric tandem allylic allyla-
tion of 11a, providing the chiral 4-benzyl-2-vinylmor-
pholine 12a or 1,4-dibenzyl-2-vinylpiperazine 12b that
are useful intermediates of biologically active com-
pounds. Further applications and modifications of the
ligands 1 and 2a–d are in progress.
S. L.; Levin, R. B. L.; Newton, C. L.; Hoffman, J. M.;
Darke, P. L.; Zugay-Murphy, J. A.; Emilio, E. A.; Schleif,
W. A.; Olsen, D. B.; Stahlhut, M. W.; Rutkowski, C. A.;
Kuo, L. C.; Lin, J. H.; Chen, I.-W.; Michelson, S. R.;
Holloway, M. K.; Huff, J. R.; Vacca, J. P. J. Med. Chem.
2000, 43, 3386–3399.
5. (a) Uozumi, Y.; Tanahashi, A.; Hayashi, T. J. Org. Chem.
1993, 58, 6826–6832; (b) Yamazaki, A.; Achiwa, K. Tetra-
hedron: Asynmmetry 1995, 5, 1021–1024.
6. For norbornane-based phosphinooxathiane ligand 13, see:
(a) Nakano, H.; Okuyama, Y.; Hongo, H. Tetrahedron
Lett. 2000, 41, 4615–4618; (b) Nakano, H.; Okuyama, Y.;
Yanagida, M.; Hongo, H. J. Org. Chem. 2001, 66, 620–
625; (c) Nakano, H.; Suzuki, Y.; Kabuto, C.; Fujita, R.;
Hongo, H. J. Org. Chem. 2002, 67, 5011–5014. For pyrro-
lidine-based phosphinooxazolidine ligand 14, see: (d)
Okuyama, Y.; Nakano, H.; Hongo, H. Tetrahedron:
Asymmetry 2000, 11. 1193–1198; (e) Nakano, H.;
Okuyama, Y.; Suzuki, Y.; Fujita, Y.; Kabuto, C. Chem.
Commun. 2002, 1146–1147.
References
1. For recent reviews including palladium-catalyzed allylic
substitution reactions; see: (a) Tsuji, J. Palladium Reagents
and Catalysis; Innovations in Organic Synthesis; Wiley:
New York, 1995; (b) Trost, B. M.; van Vranken, D. L.
Chem. Rev. 1996, 96, 395–422; (c) Johannsen, M.; Jor-
gensen, K. A. Chem. Rev. 1998, 98, 1689–1708; (d)
Hayashi, T. J. Organomet. Chem. 1999, 576, 195–202; (e)
Helmchen, G. J. Organomet. Chem. 1999, 576, 203–214.
2. (a) Janssen, J. P.; Helmchen, G. Tetrahedron Lett. 1997,
38, 8025; (b) Hayashi, T.; Kawatsura, M.; Uozumi, Y. J.
Am. Chem. Soc. 1998, 120, 1681–1687; (c) Pretot, R.;
Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1998, 37, 323–325;
(d) Yonehara, K.; Hashizume, T.; Mori, K.; Uemura, S. J.
Org. Chem. 1999, 64, 9374–9380; (e) Deng, W.-P.; Hou,
X.-L.; Dai, L.-X.; Yu, Y.-H.; Xia, W. Chem. Commun.
2000, 285–286; (f) Fuji, K.; Ohnishi, H.; Moriyama, S.;
Tanaka, K.; Kawabata, T.; Tsubaki, K. Synlett 2000, 12,
351–352; (g) Mino, T.; Hata, S.; Ohtaka, K.; Sakamoto,
M.; Fujita, T. Tetrahedron Lett. 2001, 42, 4837–4839; (h)
Stranne, R.; Vasse, J.-L.; Moberg, C. Org. Lett. 2001, 3,
2525–2528; (i) Dai, W.-M.; Yeung, K. K. Y.; Liu, J.-T.;
Zhang, Y.; Williams, I. D. Org. Lett. 2002, 4, 1615–1618.
3. Tsuda, T.; Kiyoi, T.; Saegusa, T. J. Org. Chem. 1990, 55,
3388–3390.
1
7. Ligand 2d: mp 70–73°C; [h]2D2=+46.92 (c 1.3, CHCl3); H
NMR (CDCl3): l 1.21–1.27 (m, 6H), 1.43 (s, 3H), 2.81
(dd, J=13.6, 2.5 Hz, 1H), 3.04 (dd, J=13.3, 1.9 Hz, 1H),
3.74 (m, 1H), 3.87 (q, J=13.6 Hz, 1H), 4.13 (m, 1H), 4.28
(d, J=3.6 Hz, 1H), 5.84 (d, J=7.7 Hz, 1H), 6.00 (d,
J=3.6 Hz, 1H), 6.90 (m, 1H), 7.14–7.48 (m, 17H), 7.90 (m,
1H); 13C NMR (CDCl3): l 26.21, 26.75, 43.55, 54.07,
73.67, 78.65, 83.53, 88.96(d), 105.68, 111.27, 126.10,
127.06, 127.61, 127.82, 128.10, 128.15, 128.19, 128.36,
128.46, 128.48, 128.63, 128.74, 129.49, 133.34, 133.63,
133.67, 133.78, 134.08, 136.20, 136.50, 136.64, 142.58,
142.92, 143.23. HRMS found: 565.241. Calcd for
C35H36NO4P (M+): 565.2382.
8. Typical procedure for tandem reaction (entry 3): A mix-
ture of ligand 2d (8.2 mg, 0.0145 mmol) and [PdCl(h3-
C3H5)]2 (2.7 mg, 0.004 mmol) in dry dichloromethane (3
ml) was strried at rt. After 1 h, triethylamine (0.080 ml,
0.58 mmol), 10a (0.050 ml, 0.29 mmol), and 11a (44 mg,
0.29 mmol) were added at 0°C and was stirred for 72 h.
The solvent was evaporated under reduced pressure and
the residue was purified by preparative TLC (hexane/
AcOEt=5/1) to give a pure product 12a (35.6 mg, 60%).
The enantiomeric excess was determined by HPLC (Chi-
ralcel OD-H, 0.5 ml/min, hexane/2-propanol=59/1, S-12a:
10.3 min, R-12b: 11.0 min).
4. (a) Morie, T.; Kato, S.; Harada, H.; Yoshida, N.; Mat-
sumoto, J. Chem. Pharm. Bull. 1994, 42, 877–882; (b)
Sakurai, N.; Sano, M.; Hirayama, F.; Kuroda, T.;
Uemori, S.; Moriguchi, A.; Yamamoto, K.; Ikeda, Y.;
Kawakita, T. Bioorg. Med. Lett. 1998, 8, 2185–2190; (c)
Berg, S.; Larsson, L.-G.; Renyi, L.; Ross, S. B.; Thorberg,
S.-O.; Thorell-Svantesson, G. J. Med. Chem. 1998, 41,
1934–1942; (d) Dorsey, B. D.; McDonough, C.; McDaniel,