DEDICATED CLUSTER
COMMUNICATIONS
Zirconium-Catalyzed Asymmetric Carboalumination of Alkenes
Chem. Soc., Perkin Trans. 1 2000, 367–376; g) M. Lars-
son, B.-V. Nguyen, H.-E. Hçgberg, E. Hendenstrçm,
Eur. J. Org. Chem. 2001, 2, 353–363.
(2S)-4-tert-Butyldiphenylsilyloxy-2-methyl-1-
butanol[17]
To 11.3 mL (45 mmol) of i-Bu3Al in 45 mL of CH2Cl2 was
added 0.81 mL (45 mmol) of H2O atÀ508C, and the mixture
was stirred at 238C for 1 h to give a solution of IBAO in
CH2Cl2 (Note: although IBAO[4b] was used in this case, it
may be substituted with MAO). To 602 mg (0.90 mmol) of
(+)-(NMI)2ZrCl2 in 45 mL of CH2Cl2 were added 13 mL
(135 mmol) of Me3Al. To the resultant orange mixture were
added via cannula 28.0 g (90 mmol) of 4-tert-butyldiphenylsi-
lyloxy-1-butene in 90 mL of CH2Cl2 and the IBAO solution
prepared above. After stirring for 5 h at 238C, the reaction
mixture was treated with a vigorous steam of O2 bubbled
through a needle for 1 h at 08C, and stirred further for 5 h
at 238C under O2. The reaction mixture were quenched with
2 N NaOH, extracted with CH2Cl2, the organic phase was
washed with water, dried and concentrated. Purification by
column chromatography (silica gel, 90/10 hexanes-EtOAc)
afforded the title compound mixed with its R isomer as a
colorless oil; yield: 24.0 g (78%); ꢀ98% pure by 13C NMR;
77% ee by Mosher ester analysis.
To 24.0 g (70 mmol) of the crude product of 77% ee ob-
tained above in 200 mL of CH2Cl2 were added 2.1 g of
Amano PS lipase (30 mg/mmol substrate) and 35 mL
(350 mmol) of vinyl acetate. After stirring for 24 h at 238C,
at which time 72% of the substrate was acetylated, the reac-
tion mixture was filtered, concentrated and purified by
column chromatography (silica gel, 97/3 hexanes-EtOAc) to
afford the desired acetate as a colorless oil; yield: 18.8 g
(70%).
[2] a) C.-S. Chen. Y. Fugimoto, G. Girdaukas, C. J. Sih, J.
Am. Chem. Soc. 1982, 104, 7294–7299; b) C.-S. Chen,
C. J. Sih, Angew. Chem. 1989, 711–724; Angew. Chem.
Int. Ed. 1989, 28, 695–707.
[3] a) D. Y. Kondakov, E. Negishi, J. Am. Chem. Soc. 1995,
117, 10771–10772; b) D. Y. Kondakov, E. Negishi, J.
Am. Chem. Soc. 1996, 118, 1577–1578.
[4] a) S. Huo, E. Negishi, Org. Lett. 2001, 3, 3253–3256;
b) S. Huo, J. Shi, E. Negishi, Angew. Chem. 2002, 114,
2245–2247; Angew. Chem. Int. Ed. 2002, 41, 2141–
2143.
[5] a) E. Negishi, Z. Tan, B. Liang, T. Novak, Proc. Natl.
Acad. Sci. USA 2004, 101, 5782–5787; b) Z. Tan, E.
Negishi, Angew. Chem, 2004, 116, 2971–2974; Angew.
Chem. Int. Ed. 2004, 43, 2911–2914; c) M. Magnin-La-
chaux, Z. Tan, B. Liang, E. Negishi, Org. Lett. 2004, 6,
1425–1427; d) T. Novak, Z. Tan, B. Liang, E. Negishi,
J. Am. Chem. Soc. 2005, 127, 2838–2839; e) B. Liang,
T. Novak, Z. Tan, E. Negishi, J. Am. Chem. Soc. 2006,
128, 2770–2771.
[6] For other asymmetric methods for the synthesis of de-
oxypolypropionates, see: references 6–20 in Ref.[5a]
[7] For more recent catalytic asymmetric methods, see:
a) J. Schuppan, A. J. Minnaard, B. L. Feringa, Chem.
Commun. 2004, 792–793; b) R. P. van Summeren,
S. J. W. Reijmer, B. L. Feringa, A. J. Minnaard, Chem.
Commun. 2005, 1387–1389.
[8] X. Zeng, F. Zeng, E. Negishi, Org. Lett. 2004, 6, 3245–
3248.
To 18.8 g (49 mmol) of the acetate in 150 mL of CH3OH
were added 3.2 g (50 mmol) of KOH. After stirring for 2 h
at 238C, the mixture was concentrated under vacuum, ex-
tracted with ether, washed with water, dried and concentrat-
ed again, and purified by column chromatography (silica
gel, 90/10 hexanes-EtOAc) to afford the title compound;
yield: 16.0 g (95%); 98% ee by Mosher ester analysis: [a]2D3:
À6.958 (c 1.0, CHCl3).
[9] For the synthesis of the R and S pairs of 2-methyl-3-
iodo-1-propanol, see: Ref.[5e]
[10] a) P. Wipf, S. Ribe, Org. Lett. 2000, 2, 1713–1716;
b) see also: Ref.[5d]
[11] a) H. Matsushita, E. Negishi, J. Am. Chem. Soc. 1981,
103, 2882–2884; b) E. Negishi, S. Chatterjee, H. Mat-
sushita, Tetrahedron Lett. 1981, 22, 3737–3740; c) for a
review, see: E. Negishi, F. Liu, in: Handbook of Orga-
nopalladium Chemistry for Organic Synthesis, (Ed.: E.
Negishi), Wiley, New York, 2002, chap. III. 2.9, pp 551–
589.
Acknowledgements
[12] Z. Tan, B. Liang, S. Huo, J. Shi, E. Negishi, Tetrahe-
dron: Asymmetry 2006, 17, 512–515.
[13] N. Yamazaki, W. Dokoshi, C. Kibayashi, Org. Lett.
We thank the National Science Foundation (grant: CHE-
0309613), the National Institutes of Health (grant: GM36792)
and Purdue University for support of this research. We also
thank Professor J.-E. Bäckwall for helpful suggestion.
2001, 3, 193–196.
[14] For a synthesis of ent-stellettamide A, see: a) G. A.
Whitlock, E. M. Carreira, J. Org. Chem. 1997, 62,
7916–7917; b) G. A. Whitlock, E. M. Carreira, Helv.
Chim. Acta 2000, 83, 2007–2022.
References
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Adv. Synth. Catal. 2007, 349, 539 – 545
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