5
986
J. S. Yadav et al. / Tetrahedron Letters 50 (2009) 5984–5986
(
95% ee, by HPLC analysis). After protecting the secondary alcohol
7. Nozoe, S.; Hirai, K.; Tsuda, K.; Ishibashi, K.; Shirasak, M. Tetrahedron Lett. 1965,
, 4675.
6
of enoate as the tetrahydropyranyl ether, the ester was hydrolyzed
under basic aqueous conditions and then desilylated to give the
8
9
.
.
MacMillan, J.; Simpson, T. J. J. Chem. Soc., Perkin 1 1973, 1487.
Machinaga, N.; Kibayashi, C. Tetrahedron Lett. 1993, 34, 841.
hydroxy carboxylic acid 18. Finally, compound 18 was subjected
10. Dommerholdt, E. J.; Thijs, L.; Zwanenburg, B. Tetrahedron Lett. 1991, 32, 1499.
11. Amigoni, S.; Le Floc’h, Y. Tetrahedron: Asymmetry 1997, 8, 2827.
to the Mitsunobu cyclization by Gerlach’s procedure18 for the mac-
12. Jun, I. S.; Wook Lee, J.; Sakamoto, S.; Yamaguchi, K.; Kimoon, K. Tetrahedron
rolactonization to take place with complete inversion of chirality at
Lett. 2000, 41, 471.
1
9
C-4 to furnish 19 in 58% yield. Removal of THP group (TsOH,
MeOH) gave the target macrolide 1 in 98% yield as a white solid,
13. (a) Tokunaga, M.; Larrow, J. F.; Kakiuchim, F.; Jacobsen, E. N. Science 1997, 277,
36; (b) Yadav, J. S.; Bandyopadhyay, A.; Kunwar, A. C. Tetrahedron Lett. 2001,
9
2
D
5
4a
43, 4907; (c) Yadav, J. S.; Srihari, P. Tetrahedron: Asymmetry 2004, 15, 81; (d)
Srihari, P.; Vijaya Bhasker, E.; Harshavardhan, S. J.; Yadav, J. S. Synthesis 2006,
23, 4041.
mp 136–137 °C; ½
a
ꢁ
ꢀ3.2 (c 0.25, acetone) {lit. mp 135 °C;
2
D
0
½aꢁ
ꢀ3.0 (c 1.0, acetone)}, the analytical and spectral data of the
20
14. Corey, E. J.; Marafat, A.; Laguzza, B. C. Tetrahedron Lett. 1981, 22, 3339.
compound 1 were in good agreement with the literature.
15. Brown, S. P.; Brochu, M. P.; Sinz, C. J.; MacMillan, D. W. C. J. Am Chem. Soc. 2003,
In summary, we have developed an efficient route for the syn-
thesis of pyrenophorol starting from readily available 1,6-hexane-
diol. The synthetic strategy is based on the facile tandem
1
25, 10808.
16. For other reports on proline-catalyzed oxidation of aldehydes see: (a) Zhong, G.
Angew. Chem., Int. Ed. 2003, 42, 4247; (b) Hayashi, Y.; Yamaguchi, J.; Hibino, K.;
Shoji, M. Tetrahedron Lett. 2003, 44, 8293; (c) Chandrasekhar, S.; Yaragorla, S.
R.; Sreelakhmi, L. Tetrahedron Lett. 2007, 48, 7339; (d) Zhong, G. Chem.
Commun. 2004, 606–607.
MacMillan
of key intermediate, that is,
a
-hydroxylation and HWE reaction for the construction
-hydroxy- ,b-unsaturated ester in a
c
a
single step, which allows the preparation of target molecule in a
short and efficient route.
17. (a) Zhong, G.; Yu, Y. Org. Lett. 2004, 6, 1637; (b) Mangion, I. K.; MacMillan, D. W.
C. J. Am. Chem. Soc. 2005, 127, 3697; (c) Varseev, G. N.; Maier, M. E. Org. Lett.
2007, 9, 1461.
1
1
8. Gerlach, H.; Gertle, K.; Thahnann, A. Helv. Chim. Acta 1977, 60, 2860.
9. (a) Kobayashi, Y.; Nakano, M.; Kumar, G. B.; Kishihara, K. J. Org. Chem. 1998, 63,
Acknowledgment
7
505; (b) Srinivasa Rao, K.; Srinivasa Reddy, D.; Mukkanti, K.; Manojit, P.;
Iqbala, J. Tetrahedron Lett. 2006, 47, 6623.
20. Spectral data for compound 15: Pale yellow oily liquid, ½
IR (KBr): max 3442, 2927, 2855, 1721, 1656, 1465, 1255, 1043, 774 cm
NMR (CDCl , 300 MHz): d 6.89 (dd, J = 15.8 Hz, 1H), 6.02 (dd, J = 15.8 Hz, 1H),
.28–4.20 (m, 1H), 4.18 (q, J = 14.3, 6.8 Hz, 2H), 3.94–3.87 (m, 1H), 1.74–1.52
m, 4H), 1.30 (t, J = 6.8 Hz, 3H), 1.16 (d, J = 6.8 Hz, 3H), 0.89 (s, 9H), 0.07 (s, 6H);
2
5
U.V.S.R. thanks UGC, New Delhi, for the award of a fellowship.
aꢁ
+11.6 (c 1.5, CHCl ),
D
3
ꢀ
1 1
m
; H
3
References and notes
4
(
1
3
1
2
.
.
Omura, S. Macrolide Antibiotics: Chemistry, Biology and Practice; Academic: New
York, 1984. p 538.
Karsten, K.; Umar, F.; Ulrich, F.; Barbara, S.; Siegfried, D.; Gennaro, P.; Piero, S.;
Sándor, A.; Tibor, K. Eur. J. Org. Chem. 2007, 3206.
C NMR (CDCl
25.9, 23.1, 18.1, 14.3, ꢀ4.3, ꢀ4.6; ESI-MS: m/z: 317 (M+H) ; HRMS (ESI) calcd
for C16 NaSi: 339.1967, found: 339.1974. Compound 1: white solid mp
136–138 °C; ½
1647, 1274, 1173, 1119 cm
3
, 75 MHz): d 166.3, 150.2, 120.0, 71.0, 68.4, 60.1, 35.3, 32.2,
+
32 4
H O
2
5
aꢁ
ꢀ3.2. (c 0.25, acetone) IR (KBr):
m
max 3382, 2924, 2854, 1713,
300 MHz): 6.83 (dd,
D
ꢀ
1
1
3
4
.
.
Findlay, J. A.; Li, G.; Miller, J. D.; Womiloju, T. O. Can. J. Chem. 2003, 81, 284.
(a) Kis, Z.; Furger, P.; Sigg, H. P. Experientia 1969, 25, 123; (b) Grove, J. F. J. Chem.
Soc. C 1971, 2261.
;
H
NMR (CDCl
3
,
d
J = 15.6 Hz, 2H), 5.89 (dd, J = 15.6 Hz, 2H), 5.10–5.01 (m, 2H), 4.24–4.16 (m,
2H), 2.69–2.48 (m, 2H), 2.01–1.53 (m, 8H), 1.20 (dd, J = 6.8 Hz, 6H); 13C NMR
5
6
.
.
Kind, R.; Zeeck, A.; Grabley, S.; Thiericke, R.; Zerlin, M. J. Nat. Prod. 1996, 59,
(CDCl
3
, 75 MHz): d 165.0, 149.3, 122.0, 70.3, 69.7, 30.4, 28.8, 18.2; ESI-MS: m/z:
+
5
39.
330 (M+NH ), 335 (M+Na) .
4
Christner, C.; Kullertz, G.; Fischer, G.; Zerlin, M.; Grabley, S.; Thiericke, R.;
Taddei, A.; Zeeck, A. J. Antibiot. 1998, 51, 368.