4526
M. K. Gurjar et al. / Tetrahedron Letters 45 (2004) 4525–4526
HO
HO
O
O
O
O
Ref. 6
O
4
O
a
c
g
b
D-Glucose
O
O
O
O
O
O
5
6
O
O
OH OH
O
OH
e
f
d
O
O
O
O
OH
HO
10
7
8
9
HO
PMBO
j
OH OPMB
i
h
O
O
O
O
O
O
11
12
13
1
Scheme 1. Reagents, conditions and yields: (a) 0.8% H2SO4, MeOH, rt, 12 h, (84%); (b) silica gel supported NaIO4, CH2Cl2, rt, 30 min (95%); (c)
BrꢀPþPh3CH2CH3, n-BuLi, THF, )78 to 0 °C, 3 h (82%); (d) H2, Pd/C, 1 bar, rt, 3 h (92%); (e) 20% AcOH in H2O, concd H2SO4 (catalytic), reflux,
6 h (93%); (f) IꢀPþPh3CH3, n-BuLi, THF, 0 °C to rt, 12 h (76%); (g) PMBCl, NaH, DMF, 0 °C, 1 h, (94%); (h) 5-hexenoic acid, 2,4,6-trichlorobenzoyl
chloride, DMAP, THF, 11 in THF, 0 °C to rt, 4 h (82%); (i) DDQ, CH2Cl2/H2O (18:1), rt, 30 min (94%); (j) (i) RuCl2(@CHPh)(PCy3)2, CH2Cl2,
reflux, 4 days, (36%) (52% starting material recovered), (ii) RuCl2(@CHPh)(PCy3)(IEMS), CH2Cl2, reflux, 16 h, (78%).
2. Rousseau, G. Tetrahedron 1995, 21, 2777–2849.
3. (a) For recent reviews on olefin metathesis, see: Schuster,
M.; Blechert, S. Angew. Chem., Int. Ed. 1997, 36, 2037–
2056; (b) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54,
4413–4450; (c) Armstrong, S. K. J. Chem. Soc., Perkin
Trans. 1 1998, 371–388; (d) Schrock, R. R. Tetrahedron
1999, 55, 8141–8153; (e) Wright, D. L. Curr. Org. Chem.
1999, 3, 211–240; (f) Furstner, A. Angew. Chem., Int. Ed.
2000, 39, 3012–3043; (g) Trnka, T. M.; Grubbs, R. H. Acc.
Chem. Res. 2001, 34, 18–37.
4. (a) Furstner, A.; Radkowski, K. Chem. Commun. 2001, 7,
671–672; (b) Sabino, A. A.; Pilli, R. A. Tetrahedron Lett.
2002, 43, 2819–2821; (c) Furstner, A.; Radkowski, K.;
Wirtz, C.; Goddard, R.; Lehmann, C. W.; Mynott, R. J.
Am. Chem. Soc. 2002, 124, 7061–7069.
hands, RCM of compound 12 led to the formation of
the homodimer as the major product. With the use of
precursor 13 for RCM, we could almost completely
suppress the homodimerization. The reaction of 13 with
the first generation Grubbs’ catalyst in CH2Cl2 (high
dilution) under reflux conditions gave the natural
product 1 in 36% yield as the only product after 4 days
with 52% recovery of the starting material, while the
second generation catalyst provided the final compound
1 in 78% yield (Scheme 1). Spectral and analytical data
obtained for 1 were consistent with those reported in the
literature.1
In conclusion, we have completed the first total synthesis
of the biologically active natural product herbarumin III
(1) starting from D-glucose.
5. Diez, E.; Dixon, D. J.; Ley, S. V.; Polara, A.; Rodriguez,
F. Synlett 2003, 8, 1186–1188.
6. (a) Schmidt, O. T. In Methods in Carbohydrate Chemistry;
Whistler, R. L., Wolfrom, M. L., Eds.; Academic: New
York, 1963; Vol. 2, pp 318–325; (b) Barton, D. H. R.;
McCombie, S. W. J. Chem. Soc., Perkin Trans. 1 1975,
1574–1585.
Acknowledgements
S.K. thanks CSIR, New Delhi for financial assistance in
the form of a Research Fellowship.
7. Zhong, Y. L.; Shing, T. K. M. J. Org. Chem. 1997, 62,
2622–2624.
8. Freeman, F.; Robarge, K. D. Carbohydr. Res. 1986, 154,
270–274.
References and notes
9. Krapcho, A. P. Synthesis 1982, 805–822, and 893–914.
10. Jnanaga, J.; Hirata, K.; Saeki, H.; Katsuki, T.; Yama-
guchi, M. Bull. Chem. Soc. Jpn. 1979, 52, 1989–
1993.
1. Rivero-Cruz, J. S.; Macias, M.; Cerda-Garcia, C. M.;
Mata, R. J. Nat. Prod. 2003, 66, 511–514.