1H NMR (360 MHz) and 13C NMR (90 MHz) gave expected chemical shift
values.
a-MAPI 1 was treated with NaBH4 and gave after purifica-
tion the expected alcohol 3 in 64% yield.¶ Further work in this
area is continuing.
1 S. Murao and T. Watanabe, Agric. Biol. Chem., 1977, 41, 1313.
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Notes and References
3 T. Shin-Watanabe, K. Fukuhara and S. Murao, Tetrahedron, 1982, 38,
1775.
4 R. Kaneto, H. Chiba, K. Dobashi, I. Kojima, K. Sasaki, N. Shibamoto,
H. Nishida, R. Okamoto, H. Akagawa and S. J. Mizuno, J. Antibiot.,
1993, 46, 1622.
† E-mail: RPS2@soton.ac.uk
‡ All amino acids described in this work are of l-configuration. TBos refers
to the tri-tert-butoxysilyl group.
§ Analytical and preparative reversed-phase HPLC (RP-HLPC) experi-
ments were performed on a Gilson 715 instrument equipped with a multi-
wave length detector (Applied Biosystems 759A) and two slave 306 pumps.
Retention times are given for gradient elution using the following
conditions: Column, Vydac C18 (10 mm, 0.46 and 2.2 3 25 cm); eluent A,
0.1% (v/v) TFA in H2O; eluent B, 0.1% (v/v) TFA in acetonitrile, gradient,
0% B over 2 min, 0–80% B over 32 min; flow rate 1 ml min21 (analytical)
and 10 ml min21 (preparative); absorbance, 216 nm. Molecular weight
determinations were carried out by electrospray (ES) Micromass Quattro II
mass spectrometer.
¶ All compounds reported herein are white solids and exhibited satisfactory
analytical and spectral data. Selected data for a-MAPI-diol 4: single peak,
retention time, 16.5 min HPLC; ESMS, m/z 628 [M + H]+. Selected data for
a-MAPI 1: single peak, retention time, 16.8 min HPLC; mp 211–213 °C
(decomp.) (lit.,2 204–205 °C); [a]2D4 22.2 (c 0.9, AcOH) (lit.,2 218); ESMS,
m/z 596 [M + H]+ and 614 [M + H2O]+, hemi-acetal; dH (360 MHz,
[2H7]DMF) 0.79 (d, 3H, J 6.7 CH–CH3, Val), 0.81 (d, 3H, J 6.9, CH-CH3,
Val), 1.5–1.75 (m, 4H, CH–CH2–CH2, Arg), 2.08 (h, 1H, J 6.55, CH[CH3]2,
Val), 3.0–3.35 (m, 4H, 2 3 CH2, Phe), 3.6 (2H, obscured by solvent, –CH2–
NH, Arg), 4.3–4.6 (m, 4H, 4 3 methines), 6.5 (d, 1H, J 8), 6.7 (d, 1H, J 7.8),
7.2 (m, 10H, 2 3 C6H5, Phe), 7.55 (br), 7.85 (d, 1H, J 8.6), 8.5 (d, 1H, J 7.1),
9.58 (s, 1H, CHO). Selected data for alcohol 3: single peak, retention time,
16.8 min HPLC; mp 155 °C, softens and 180–182 °C, (decomp. lit.,5
182 °C); [a]2D4 224.0 (c 0.5, AcOH) (lit.,5 –24.4); ESMS, m/z 598 [M + H]+;
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Received in Cambridge, UK, 27th March 1998; 8/02380H
1450
Chem. Commun., 1998