K. Watanabe et al. / Journal of Organometallic Chemistry 581 (1999) 103–107
107
for 2 h and then heated under reflux for another 1 h.
References
The solution was cooled, and all volatile components
were removed in vacuo. The resulting allylboronate 7
was dissolved in THF (10 ml) and then used for the
enantioselective allylboration reaction.
[1] (a) D. Enders, U. Reinhold, Tetrahedron: Asymmetry 8 (1997)
1895. (b) S.E. Denmark, O.J.-C. Nicaise, Chem. Commun.
(1996) 999.
[2] H. Moser, G. Rihs, H. Santer, Z. Naturforsch. 376 (1982) 451.
[3] J.K. Whitesell, Chem. Rev. 89 (1989) 1581.
[4] M. Nakamura, A. Hirai, E. Nakamura, J. Am. Chem. Soc. 118
(1996) 8489.
3.3.3. Chirally modified B-allyloxazaborolidine (8)
According to the procedure described before [11b], 8
was prepared from the N-sulfonylamino alcohol,
derived from (−)-norephedorine with triallylborane in
THF.
[5] G. Cainelli, M. Panunzio, P. Andreoli, G. Martelli, G. Spunta,
D. Giacomini, E. Bandini, Pure & Appl. Chem. 62 (1990) 605.
[6] (a) D.H. Hua, S.W. Miao, J.S. Chen, S. Iguchi, J. Org. Chem. 56
(1991) 4. (b) R.G. Lovey, A.B. Cooper, Synlett (1994) 167. (c)
T.-K. Yang, R.-Y. Chen, D.-S. Lee, W.-S. Peng, Y.-Z. Jiang,
A.-Q. Mi, T.-T. Jong, J. Org. Chem. 59 (1994) 914.
[7] (a) T. Suzuki, Y. Hirokawa, K. Ohtake, T. Shibata, K. Soai,
Tetrahedron: Asymmetry 8 (1997) 4033. (b) A.A. Cantrill, A.N.
Jarvis, H.M.I. Osborn, A. Ouadi, J.B. Sweeney, Synlett. (1996)
847.
3.4. Enantioselecti6e allylboration of
N-diisobutylaluminum imine 2a with chirally modified
allylboron reagent 5
[8] (a) D.J. Hart, K. Kanai, D.G. Thomas, T.-K. Yang, J. Org.
Chem. 48 (1983) 289. (b) S. Itsuno, H. Yanaka, C. Hachisuka,
K. Ito, J. Chem. Soc., Perkin Trans. 1 (1991) 1341.
[9] (a) S. Itsuno, C. Hachisuka, K. Ito, J. Chem. Soc., Perkin Trans.
1 (1991) 1767. (b) S. Itsuno, C. Hachisuka, K. Kitano, K. Ito,
Tetrahedron Lett. (1992) 627. (c) S. Istuno, C. Hachisuka, Y.
Ushijima, K. Ito, Synthetic Commun. 22 (1992) 3229.
[10] S. Itsuno, M. Sasaki, S. Kuroda, K. Ito, Tetrahedron: Asymme-
try 6 (1995) 1531.
[11] (a) S. Itsuno, K. Watanabe, K. Ito, A.A. El-Shehawy, A.A.
Sarhan, Angew. Chem. Int. Ed. Engl. 36 (1997) 109. (b) K.
Watanabe, K. Ito, S. Itsuno, Tetrahedron: Asymmetry 6 (1995)
1531.
[12] P. Andreoli, G. Cainelli, M. Contento, D. Giacomini, G.
Martelli, M. Panunzio, J. Chem. Soc. Perkin Trans. 1 (1988) 945.
[13] J.R. Zietz Jr., G.C. Robinson, K.L. Lindsay, Compr.
Organomet. Chem. 7 (1982) 431.
[14] P. Andreoli, L. Billi, G. Cainelli, M. Panunzio, G. Martelli, G.
Spunta, J. Org. Chem. 55 (1990) 4199.
[15] G. Cainelli, E. Mezzina, M. Panunzio, Tetrahedron Lett. 31
(1990) 3481.
[16] Y.N. Bubnov, in G.W. Kabalka (Ed.), Current Topics in the
Chemistry of Boron, Royal Society of Chemistry, Cambridge,
1994, p. 44.
[17] D.J. Hart, K. Kanai, D.G. Thomas, T. -K. Yang, J. Org. Chem.
48 (1983) 289.
[18] H.C. Brown, P.V. Ramachandran, Pure & Appl. Chem. 63
(1991) 307 and references cited therein.
To a solution of 5 (6 mmol) prepared from (−)-DIP-
Cl (1.92g, 6 mmol) and allylmagnesium chloride (6
mmol), a THF solution of 2a prepared from benzoni-
trile (0.5 ml, 5 mmol) and DIBAL-H (4.95 ml, 5 mmol)
in THF (5 ml) was added. The reaction mixture was
then stirred for 5 h at r.t., and quenched with 2M HCl.
The aqueous layer was separated, washed with ether,
neutralized with NH4OH and extracted with ether. The
combined extracts were dried over MgSO4 and concen-
trated by rotary evaporator to yield a colorless oil
which is essentially pure 1-phenyl-3-butenamine (0.49 g,
67%). 1H-NMR (270 MHz, CDCl3) l 7.34–7.22 (m,
5H), 5.81–5.70 (m, 1H), 5.15–5.06 (m, 2H), 3.98 (dd,
J=7.81 and 5.37 Hz, 1H), 2.46–2.32 (m, 2H), 1.53 (br,
2H); IR 3300 (NH2), 1630 (CꢀC), 1300 (C–N). The
product was purified by flash-column chromatography
on silica gel (ether). The enantioselectivity 69% ee was
determined by HPLC analysis using a chiral stationary
phase column (Daicel, Chiralcel OD-H; hexane:2-
propanol:diethylamine = 90:10:0.1, flow rate; 0.5 ml
min−1): tR 16.3 min (R), tR 20.7 min (S). The absolute
configuration of the product was correlated to that
described in the literature [26].
[19] U.S. Racherla, H.C. Brown, J. Org. Chem. 56 (1991) 401.
[20] W.R. Roush, L.K. Hoong, M.A.J. Palmer, J.C. Park, J. Org.
Chem. 55 (1990) 4109.
[21] W.R. Roush, L.K. Hoong, M.A.J. Palmer, J.A. Straub, A.D.
Palkowitz, J. Org. Chem. 55 (1990) 4117.
Acknowledgements
[22] S. Itsuno, A.A. El-Shehawy, A.A. Sarhan, Reactive & Func-
tional Polym. 37 (1998) 283.
[23] H.C. Brown, P.K. Jadhav, J. Am. Chem. Soc. 105 (1983) 2092.
[24] U.S. Racherla, H.C. Brown, J. Org. Chem. 56 (1991) 401.
[25] W.R. Roush, A.E. Walts, L.K. Hoong, J. Am. Chem. Soc. 107
(1985) 8186.
This work was partially supported by a Grant-in-Aid
for Scientific Research from the Ministry of Education,
Science, Sports, and Culture, Japan and The Mitsubishi
Petrochemical (Mitsubishi Chemical) Foundation. The
Yamanouchi Award in Synthetic Organic Chemistry,
Japan (to S.I.) is also gratefully acknowledged.
[26] T. Basile, A. Bocoum, D. Savoia, A. Umani-Ronchi, J. Org.
Chem. 59 (1994) 7766.
.