chromatography, using 2 : 3 ethyl acetate–pentane as eluent, to
give salinosporamide A (3.6 mg, 45% over the three steps) as a
colourless solid; mp 169–172 ◦C (from ethyl acetate–pentane);
dH (360 MHz, C5D5N) 10.60 (1H, br s, NH), 6.41 (1H, d, J
(h) C. H. Yoon, D. L. Flanigan, K. S. Yoo and K. W. Jung, Eur. J. Org.
Chem., 2007, 37–39; (i) C. B. Gilley, M. J. Buller and Y. Kobayashi,
Org. Lett., 2007, 9, 3631–3636; (j) J.-C. Legeay and N. Langlois, J. Org.
Chem., 2007, 72, 10108–10113.
6 L. R. Reddy, P. Saravanan and E. J. Corey, J. Am. Chem. Soc., 2004,
126, 6230–6231.
=
=
10.5, CH CHCH), 5.88 (1H, m, CH CHCH), 4.91 (1H, br s,
OH), 4.25 (1H, app. t, J 9.0, CH(OH)), 4.13 (1H, app. td, J
6.8 and 10.7, CH2CHHCl), 4.01 (1H, app. td, J 6.8 and 10.7,
7 A. Endo and S. J. Danishefsky, J. Am. Chem. Soc., 2005, 127, 8298–
8299.
8 T. Ling, V. R. Macherla, R. R. Manam, K. A. McArthur and B. C. M.
Potts, Org. Lett., 2007, 9, 2289–2292.
9 (a) V. Caubert, J. Masse´, P. Retailleau and N. Langlois, Tetrahedron
Lett., 2007, 48, 381–384; (b) V. Caubert and N. Langlois, Tetrahedron
Lett., 2006, 47, 4473–4475.
10 G. Ma, H. Nguyen and D. Romo, Org. Lett., 2007, 9, 2143–2146.
11 Preliminary communication: N. P. Mulholland, G. Pattenden and
I. A. S. Walters, Org. Biomol. Chem., 2006, 4, 2845–2846. The synthesis
of ( )-salinosporamide A described by Romo et al. (ref. 10) also has
implications for the biosynthesis of the natural product.
12 For recent studies of the biosynthesis of salinosporamide A, see:
L. L. Beer and B. S. Moore, Org. Lett., 2007, 9, 845–848, and for
earlier studies of the biosynthesis of lactacystin, see: A. Nakagawa,
S. Takahashi, K. Uchida, K. Matsuzaki, S. Omura, A. Nakamura,
N. Kurihara, T. Nakamatsu, Y. Miyake, K. Take and M. Kainosho,
Tetrahedron Lett., 1994, 35, 5009–5012.
=
CH2CHHCl), 3.17 (1H, app. t, J 7.0, CHC( O)NH), 2.84 (1H,
=
br s, CH CHCH), 2.48 (1H, m, CHHCH2Cl), 2.37–2.26 (2H,
=
m, CHHCH2Cl and CHCH(R)CHH), 2.07 (3H, s, CCH3),
1.91 (2H, m, CH2CH CHCH), 1.73–1.64 (2H, CHHCH2C(R)H,
CHCH(R)CHH), 1.36 (1H, m, CHHCH2C(R)H); dC (90 MHz,
C5D5N) 176.9 (s), 169.5 (s), 129.1 (d), 128.7 (d), 86.3 (s), 80.4 (s),
71.0 (d), 46.2 (d), 43.3 (t), 39.3 (d), 29.0 (t), 26.5 (t), 25.4 (t), 21.8 (t),
20.0 (q); m/z (ES) 336.0957 (M + Na+, C15H20ClNO4Na requires
336.0973).
=
=
Acknowledgements
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We thank AstraZeneca for financial support (studentship to
N. P. M.).
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