1946
H. Sato et al. / Tetrahedron Letters 49 (2008) 1943–1947
intermediate 230. The attempted deprotection of 23 with
TMSBr, which was reported to be effective for the clean
deprotection of an allylic MOM ether,19 also resulted in
the formation of a mixture of 25a,b and/or 26a,b. These
results clearly showed that the allylic alcohol moiety in
23 is unexpectedly labile under the acidic conditions.
To avoid the formation of the allyl cation 230, the cou-
pling reaction of substrates possessing protecting groups,
which could be removed under basic conditions, was next
investigated. To our delight, the Negishi coupling of an
alkyl zinc derived from the SEM-ether 3b with c-lactone
2, followed by acetylation, successfully provided 27 in
44% yield. The treatment of 27 with anhydrous Bu4NF
and MS4A in DMPU20 at 80 °C, followed by acetylation,
provided 25b as a single isomer in 38% yield.21 The spectral
data (1H and 13C NMR) as well as the [a]D value of the syn-
thetic 25b were completely identical with those already
reported.1a Finally, alkaline hydrolysis of 25b furnished
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37–49.
28
mycestericin A (1) in 80% yield. The [a]D value {½aꢁD
ꢀ9.1 (c 0.16, MeOH); lit.1a [a]D ꢀ8.5 (c 0.50, MeOH)} as
well as spectroscopic data showed a good agreement with
those reported for the natural product.1a
In summary, the first total synthesis of mycestericin A
(1) starting from tartrates has been accomplished. This syn-
thesis fully confirmed the proposed absolute structure of
the natural product, and provided a new synthetic pathway
to highly oxygenated a-substituted a-amino acid deriva-
tives showing potent biological activities starting from
readily available tartrates.
5. Chida, N.; Takeoka, J.; Tsutsumi, N.; Ogawa, S. J. Chem. Soc.,
Chem. Commun. 1995, 793–794; Chida, N.; Takeoka, J.; Ando, K.;
Tsutsumi, N.; Ogawa, S. Tetrahedron 1997, 53, 16287–16298.
6. For an excellent review on Overman rearrangement and related
reactions, see: Overman, L. E.; Carpenter, N. E. In Organic Reactions;
Overman, L. E., Ed.; Wiley: New York, NY, 2005; Vol. 66, pp
1–107.
Acknowledgment
This work was supported in part by Grant-in-Aid for
the 21st Century COE Program ‘Keio Life Conjugate
Chemistry’ from the Ministry of Education, Culture,
Sports, Science, and Technology, Japan.
´
´
7. Sanchez-Sancho, F.; Valverde, S.; Herradon, B. Tetrahedron: Asym-
metry 1996, 7, 3209–3246.
8. All new compounds described in this Letter were characterized by
1
300 MHz H NMR, 75 MHz 13C NMR, IR, and mass spectrometric
and/or elemental analyses.
9. Nishikawa, T.; Asai, M.; Ohyabu, N.; Isobe, M. J. Org. Chem. 1998,
63, 188–192.
Supplementary data
10. The optical purities of 10, 3a, and 3b were all determined to be >99%
ee, by a chiral column analysis (Chiralcel OD-H), confirming that no
racemization had occurred during the preparation of these
compounds.
11. Keck, G. E.; Boden, E. P. Tetrahedron Lett. 1984, 25, 265–268;
Marshall, J. A. Chem. Rev. 2000, 100, 3163–3186.
1
The spectrum data and H and 13C NMR spectra of
compounds 9, 10, 11, 4, 13, 15, 2, 3a, 3b, 23, 27, 25b, and
1. Supplementary data associated with this article can be
12. Ohba, S.; Sato, H.; Iida, M.; Chida, N. Acta Crystallogr., Sect. E
2003, E59, o1259–o1260.
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