Y. Hamada et al. / Tetrahedron Letters 42 (2001) 1297–1299
1299
CONHPh
Ph
1609. (e) Tye, H.; Smyth, D.; Eldred, C.; Wills, M. J.C.S.
Chem. Commun. 1997, 1053–1054.
1) NaCl, DMSO,
160°C, 3 h
CH(CO2Me)2
Ph
2) aq. NaOH
7. For cyclic substrates, see (a) Ref. 6b. (b) Ref. 6c. (c)
Trost, B. M.; VanVranken, D. L. Angew. Chem., Int. Ed.
Engl. 1992, 31, 228–230. (d) Gilbertson, S. R.; Genov, D.
G.; Rheigold, A. L. Organic Lett. 2000, 2, 2885–2889. (e)
Gilbertson, S. R.; Collibee, S. E.; Agarkov, A. J. Am.
Chem. Soc. 2000, 122, 6522–6523. (f) Evans, D. A.;
Campos, K. R.; Tedrow, J. S.; Michael, F. E.; Gagne, M.
R. J. Am. Chem. Soc. 2000, 122, 7905–7920.
3) aniline, BopCl,
Et3N, CH2Cl2
2b
Figure 2.
8. (a) Mori, M.; Kuroda, S.; Zhang, C.-S.; Sato, Y. J. Org.
Chem. 1997, 62, 3263–3270; (b) Nishimata, T.; Mori, M.
J. Org. Chem. 1998, 63, 7586–7587; (c) Nishimata, T.;
Yamaguchi, K.; Mori, M. Tetrahedron Lett. 1999, 40,
5713–5716.
Acknowledgements
This work was financially supported in part by Grants-
in-Aid for Scientific Research (B) from the Ministry of
Education, Science, Sports and Culture, Japan and
Uehara Memorial Foundation (to Y.H.).
9. Typical procedure for the asymmetric allylic substitution
reaction: to a stirred mixture of Pd(dba)2 (41 mg, 0.071
mmol) and lithium acetate (236 mg, 3.57 mmol) in
dichloroethane (12 ml) under an argon atmosphere at
0°C was added a 0.1 M solution of (−)-9-PBN and the
mixture was stirred at 0°C for 30 min. then the mixture
was cooled to −15°C and dimethyl malonate (1.23 ml,
10.7 mmol), the methylcarbonate (830 mg, 3.57 mmol),
BSA (2.6 ml, 10.7 mmol), and dichloroethane (12 ml)
were added. The mixture was allowed to warm to 23°C
and stirred at 23°C for 4 h. After removal of the volatiles,
the mixture was diluted with ethyl acetate/hexane (1:5,
180 ml), washed with 1 M KHSO4, water, and brine,
dried over MgSO4, and concentrated in vacuo to leave a
yellow oil. The residue was chromatographed on silica gel
References
1. For reviews, see (a) Frost, C. G.; Howarth, J.; Williams,
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Trost, B. M.; Van Vranken, D. L. Chem. Rev. 1996, 96,
395–422.
2. Hamada, Y.; Seto, N.; Ohmori, H.; Hatano, K. Tetra-
hedron Lett. 1996, 37, 7565–7568.
3. For correlation with the stereostructure of 9-PBN, (S)
and (R) represent the stereochemistry of the chiral carbon
adjacent to the phosphorus atom of 9-PBN.
4. Hamada, Y.; Seto, N.; Takayanagi, Y.; Nakano, T.;
Hara, O. Tetrahedron Lett. 1999, 40, 7791–7794.
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using hexane/ethyl acetate (8:1) to give the product (915
neat
mg, 97%) as a colorless oil: IR w
3022, 1735, 1637
max
cm−1. H NMR (400 MHz, CDCl3): l 1.59–1.94 (5H, m),
2.18–2.23 (2H, m), 3.22 (3H, s), 3.56 (1H, s), 3.65 (3H, s),
5.92 (1H, m) 7.18–7.37 (5H, m).
1
6. For selected examples of acyclic substrates, see (a) Trost,
B. M.; Dietsche, T. J. J. Am. Chem. Soc. 1973, 95,
8200–8201. (b) Hayashi, T.; Yamamoto, A.; Hagihara,
T.; Ito, Y. Tetrahedron Lett. 1986, 27, 191–194. (c)
Hayashi, T.; Kishi, K.; Yamamoto, A.; Ito, Y. Tetra-
hedron Lett. 1990, 31, 1743–1746. (d) Nordstrom, K.;
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10. The alkylated product 2b was transformed to the anilide
in 3 steps as shown in Fig. 2 and analyzed by HPLC.
11. 3b: mp 104–106°C (ether-n-hexane); [h]2D5+84.2 (c 1.59,
MeOH). Crystal data for 3b: C23H27NOA, S, F.W. 413.5,
,
orthorhombic, space group P212121, a=8.753 (1) A, b=
3
,
,
,
10.373 (1) A, c=24.528 (1) A, V=2227.0 (2) A , Z=8,
Nonius Kappa CCD, Mo Kh, R=0.0508, Rw=0.0536.
.
.