S. C. Case-Green et al. / Tetrahedron: Asymmetry 19 (2008) 2620–2631
2631
R. J.; Macleod, J. K.; Coote, S. J.; Davies, S. G.; Gravatt, G. L.; Dordor-Hedgecock, I.
M.; Whittaker, M. Tetrahedron 1988, 44, 1637; (j) Davies, S. G.; Middlemiss, D.;
Naylor, A.; Wills, M. Tetrahedron Lett. 1989, 30, 587; (k) Davies, S. G.;
Middlemiss, D.; Naylor, A.; Wills, M. Chem. Commun. 1990, 797; (l) Davies, S.
G.; Polywka, R.; Warner, P. Tetrahedron 1990, 46, 4847; (m) Collingwood, S. P.;
Davies, S. G.; Preston, S. C. Tetrahedron Lett. 1990, 31, 4067; (n) Davies, S. G.
Aldrichim. Acta 1990, 23, 31; (o) Bodwell, G. J.; Davies, S. G. Tetrahedron:
Asymmetry 1991, 2, 1075; (p) Bodwell, G. J.; Davies, S. G.; Mortlock, A. A.
Tetrahedron 1991, 47, 10077; (q) Beckett, R. P.; Davies, S. G.; Mortlock, A. A.
Tetrahedron: Asymmetry 1992, 3, 123; (r) Case-Green, S. C.; Costello, J. F.;
Davies, S. G.; Heaton, N.; Hedgecock, C. J. R.; Humphries, V. M.; Metzler, M. R.;
Prime, J. C. J. Chem. Soc., Perkin Trans. 1 1994, 933; (s) Davies, S. G.; Kellie, H. M.;
Polywka, R. Tetrahedron: Asymmetry 1994, 5, 2563.
with CH2Cl2 (3 ꢃ 2 mL) and removal of the solvent in vacuo gave a
colourless oil, which was purified via column chromatography (sil-
ica, eluent 30–40 °C petrol/Et2O, 1:1) to give 6 as a white solid
(45 mg, 65%); mp 55–56 °C (lit.40 mp 55–56 °C); ½a 2D0
¼ ꢀ31:5 (c
ꢁ
0.5 in CHCl3); {lit.10
½
a 2D3
ꢁ
¼ ꢀ32 (c 0.3 in CHCl3); lit.36
½
a 2D3
ꢁ
¼ ꢀ33:7 (c 0.1 in CHCl3)}; mmax (KBr) 3430 (N–H), 1820,
1725, 1690 (3 ꢃ C@O); dH (500 MHz, CDCl3) 0.87 (6H, m, C(7)H3,
C(600)H3), 0.91 (3H, d, J 6.9, CH(CH3)A), 0.98 (3H, d, J 6.9, CH(CH3)B),
1.23–1.44 (14H, m, 7 ꢃ CH2), 1.56–1.82 (4H, m, 2 ꢃ CH2), 2.01 (1H,
m, CH(CH3)2), 2.20 (2H, m, C(1)H2), 3.22 (1H, td, J, 7.9, 4.0, C(30)H),
4.28 (1H, m, C(20)H), 4.61 (1H, dd, J 9.0, 4.8, CHNH), 5.01 (1H, m,
C(2)H), 6.24 (1H, d, J 8.8, NH), 8.25 (1H, s, CHO); dC (125 MHz,
CDCl3) 13.8, 13.9, 17.4, 19.2, 22.3, 22.4, 24.7, 26.6, 27.6, 28.9,
30.9, 31.4, 33.8, 38.6, 55.9, 57.0, 72.8, 74.5, 160.9, 170.8.
14. (a) Broadley, K.; Davies, S. G. Tetrahedron Lett. 1984, 25, 1743; (b) Davies, S. G.;
Dodor-Hedgecock, I. M.; Sutton, K. H.; Walker, J. C. Tetrahedron 1986, 18, 5123;
(c) Davies, S. G.; Dordor-Hedgecock, I. M.; Sutton, K. H.; Walker, J. C.
Tetrahedron Lett. 1986, 27, 3787.
15. Case-Green, S. C.; Davies, S. G.; Hedgecock, C. J. R. Synlett 1991, 779.
16. Aktogu, N.; Felkin, H.; Davies, S. G. J. Chem. Soc., Chem. Commun. 1982, 1303.
17. Davies, S. G.; Dordor-Hedgecock, I. M.; Warner, P. Tetrahedron Lett. 1985, 26,
2125.
References
18. The (R)-a-methylbenzylamine used for derivatisation was determined to be of
99% ee. An analogous reaction was also carried out using racemic b-lactone 13
producing a 50:50 mixture of diastereoisomeric amides, thus confirming that a
resolution process was not occurring. For a related example, see: Giresbeck, A.;
Seebach, D. Helv. Chim. Acta 1987, 70, 1326.
1. (a) Pommier, A.; Pons, J.-M. Synthesis 1995, 729; (b) Yang, H. W.; Zhao, C.;
Romo, D. Tetrahedron 1997, 53, 16471; (c) Yang, H. W.; Romo, D. Tetrahedron
1999, 55, 6403.
2. (a) Hogan, S.; Fleury, A.; Hadvary, P.; Lengsfeld, H.; Meier, M. K.; Triscari, J.;
Sullivan, A. C. Int. J. Obesity 1987, 11, 35; (b) Fernandez, E.; Borgström, B.
Biochem. Biophys. Acta 1989, 1001, 249; (c) Fernandez, E.; Borgström, B. Lipids
1990, 25, 549; (d) Hermier, D.; Hales, P.; Brindley, D. N. FEBS Lett. 1991, 286, 186.
3. (a) Weibel, E. K.; Hadvary, P.; Hochuli, E.; Kupfer, E.; Lengsfield, H. J. Antibiot.
1987, 40, 1081; (b) Hochuli, E.; Kupfer, E.; Maurer, R.; Meister, W.; Mercadal, Y.;
Schmidt, K. J. Antibiot. 1987, 40, 1086.
19. Mulzer, J.; Kerkmann, T. J. Am. Chem. Soc. 1980, 102, 3620.
20. For examples, see: (a) Noyori, R.; Ohkuma, T.; Kitamura, M.; Tanaya, H.; Sayo,
N.; Kumobyashi, H.; Akutagawa, S. J. Am. Chem. Soc. 1987, 109, 5856; (b) Ohta,
T.; Tanaya, H.; Noyori, R. Inorg. Chem. 1988, 27, 566; (c) Noyori, R.; Ikeda, T.;
Ohkuma, T.; Widhalm, M.; Kitamura, M.; Tanaya, H.; Akutagawa, S.; Sayo, N.;
Saito, T.; Taketomi, T.; Kumobyashi, H. J. Am. Chem. Soc. 1989, 111, 9134; (d)
Kitamura, M.; Tokunaga, M.; Ohkuma, T.; Noyori, R. Tetrahedron Lett. 1991, 32,
4163; (e) Burk, M. J.; Harper, T. G. P.; Kalberg, C. S. J. Am. Chem. Soc. 1995, 117,
4423; (f) Ratovelomanana-Vidal, V.; Girard, C.; Touati, R.; Tranchier, J. P.; Ben
Hassine, B.; Genêta, J. P. Adv. Synth. Catal. 2003, 345, 261; (g) Bauer, J.;
Brandenburg, K.; Zähringer, U.; Rademann, J. Chem. Eur. J. 2006, 12, 7116.
21. The ee of methyl (S)-3-hydroxytetradecanoate 34 was determined by 1H NMR
spectroscopic analysis in the presence of 0.3 equiv of the chiral solvating agent
(+)-Eu(hfc)3, and by comparison with an authentic racemic sample which was
prepared by reduction of b-keto ester 33 with NaBH4.
22. Utaka, M.; Watabu, H.; Higashi, H.; Sakai, T.; Tsuboi, S.; Torii, S. J. Org. Chem.
1990, 55, 3917.
23. Dess, D. B.; Martin, J. C. J. Org. Chem. 1983, 48, 4156.
24. (a) Barbier, P.; Schneider, F. Helv. Chim. Acta 1987, 70, 196; (b) Barbier, P.;
Schneider, F.; Widmer, U. Helv. Chim. Acta 1987, 70, 1412.
25. Davies, S. G.; Dordor, I. M.; Warner, P. J. Chem. Soc., Chem. Commun. 1984,
956.
4. Borgström, B. Biochem. Biophys. Acta 1988, 962, 308.
5. (a) Landl, J. J., Jr.; Garofolo, L. M.; Ramig, K. Tetrahedron Lett. 1993, 34, 277; (b)
Wedler, C.; Costisella, B.; Schick, H. J. Org. Chem. 1999, 64, 5301; (c) Honda, T.;
Endo, K.; Ono, S. Chem. Pharm. Bull. 2000, 48, 1545; (d) Polkowska, J.;
Łukaszewicz, E.; Kiegiel, J.; Jurczak, J. Tetrahedron Lett. 2004, 45, 3873.
6. (a) Barbier, P.; Schneider, F. Helv. Chim. Acta 1987, 70, 196; (b) Barbier, P.;
Schneider, F. J. Org. Chem. 1988, 53, 1218; (c) Hanessian, S.; Tehim, A.; Chen, P. J.
Org. Chem. 1993, 58, 7768; (d) Paterson, I.; Doughty, V. A. Tetrahedron Lett.
1999, 40, 393; (e) Yadav, J. S.; Rao, K. V.; Reddy, M. S.; Prasad, A. R. Tetrahedron
Lett. 2006, 47, 4393; (f) Yadav, J. S.; Reddy, M. S.; Prasad, A. R. Tetrahedron Lett.
2006, 47, 4995; (g) Yadav, J. S.; Rao, K. V.; Prasad, R. S. Synthesis 2006, 3888.
7. (a) Barbier, P.; Schneider, F.; Widmer, U. Helv. Chim. Acta 1987, 70, 1412; (b)
Pons, J.-M.; Kocien´ ski, P. Tetrahedron Lett. 1989, 30, 1833; (c) Fleming, I.;
Larwence, N. J. Tetrahedron Lett. 1990, 31, 3645; (d) Case-Green, S. C.; Davies, S.
G.; Hedgecock, C. J. R. Synlett 1991, 781; (e) Chadha, N. K.; Batcho, A. D.; Tang, P.
´
C.; Courtney, L. F.; Cook, C. M.; Wovkulich, P. M.; Uskokovic, M. R. J. Org. Chem.
26. The diastereoselectivity of the asymmetric aldol reaction was determined by
31P NMR spectroscopy which enabled a diastereoisomeric ratio of 96:3:1 to be
determined.
1991, 56, 4714; (f) Giese, B.; Roth, M. J. Braz. Chem. Soc. 1996, 7, 243; (g)
Fleming, I.; Larwence, N. J. J. Chem. Soc., Perkin Trans. 1 1998, 2679; (h) Ghosh, A.
K.; Liu, C. Chem. Commun. 1999, 1743; (i) Dirat, O.; Kouklovsky, C.; Langlois, Y.
Org. Lett. 1999, 1, 753; (j) Ghosh, A. K.; Fidanze, S. Org. Lett. 2000, 2, 2405; (k)
Bodkin, J. A.; Humphries, E. J.; McLeod, M. D. Aust. J. Chem. 2003, 56, 795; (l)
Thadani, A. N.; Batey, R. A. Tetrahedron Lett. 2003, 44, 8051; (m) Bodkin, J. A.;
Humphries, E. J.; McLeod, M. D. Tetrahedron Lett. 2003, 44, 2869; (n) Ma, M.;
Zancanella, Y.; Oyola, R. D.; Richardson, J.; Smith, W.; Romo, D. Org. Lett. 2006,
8, 4497; (o) Kumaraswamy, G.; Markondaiah, B. Tetrahedron Lett. 2008, 49, 327.
8. One further reference reports the synthesis of tetrahydrolipstatin 3; in this
article a 1:1 mixture of diastereoisomers is obtained, although the details of
their separation are not included. See: Parsons, P. J.; Cowell, J. K. Synlett 2000,
107.
27. Flemming, I.; Larwence, N. J. Tetrahedron Lett. 1990, 31, 3645.
28. Barbier, P.; Schneider, F.; Widmer, U. Helv. Chim. Acta 1987, 70, 1412.
29. An authentic sample of tetrahydrolipstatin 3 was kindly supplied by Dr. M.
Karpt and Dr. U. Zutter of Hoffman-La Roche.
30. The ee of methyl (S)-3-hydroxyoctanate 43 was determined by 1H NMR
spectroscopic analysis in the presence of 0.3 equiv of the chiral solvating agent
(+)-Eu(hfc)3, and by comparison with an authentic racemic sample which was
prepared by reduction of b-keto ester 42 with NaBH4.
31. Utaka, M.; Watabu, H.; Higashi, H.; Sakai, T.; Tsuboi, S.; Torii, S. J. Org. Chem.
1990, 55, 3817.
32. The diastereoselectivity of the asymmetric aldol reaction was determined by
31P NMR spectroscopy; comparison with authentic samples of the minor
diastereoisomers (and analogues produced during the synthesis of
9. Kitahara, M.; Asano, M.; Naganawara, H.; Maeda, K.; Hamada, M.; Aoyagi, T.;
Umezawa, H.; Itiaka, H. Y.; Nakamura, H. J. Antibiot. 1987, 40, 1647.
10. Bates, R. W.; Fernández-Moro, R.; Ley, S. V. Tetrahedron 1991, 47, 9929.
11. (a) Wu, Y.; Sun, Y.-P. J. Org. Chem. 2006, 71, 5748; (b) Ma, G.; Zancanella, M.;
Oyola, Y.; Richardson, R. D.; Smith, J. W.; Romo, D. Org. Lett. 2006, 8, 4497.
12. Baker, R. W.; Davies, S. G. Tetrahedron: Asymmetry 1993, 4, 1479.
13. (a) Davies, S. G.; Aktogu, N.; Felkin, H.; Baird, G. J.; Watts, O. J. Organomet. Chem.
1984, 262, 49; (b) Baird, G. J.; Davies, S. G.; Jones, R. H.; Prout, K.; Warner, P.
Chem. Commun. 1984, 745; (c) Davies, S. G.; Walker, J. C. Chem. Commun. 1985,
209; (d) Davies, S. G.; Dordor-Hedgecock, I. M.; Warner, P.; Jones, R. H.; Prout,
K. J. Organomet. Chem. 1985, 285, 213; (e) Brown, S. L.; Davies, S. G.; Foster, D.
F.; Seeman, J. I.; Warner, P. Tetrahedron Lett. 1986, 27, 623; (f) Bashiardes, G.;
Davies, S. G. Tetrahedron Lett. 1987, 28, 5563; (g) Davies, S. G. Pure Appl. Chem.
1988, 60, 13; (h) Becket, R. P.; Davies, S. G. Chem. Commun. 1988, 160; (i) Capon,
tetrahydrolipstatin 3) enabled
a diastereoisomeric ratio of 93:5:2 to be
determined.
33. Zhu, C.; Shen, X.; Nelson, S. G. J. Am. Chem. Soc. 2004, 126, 5352.
34. Tai, A.; Harada, T.; Hiraki, Y.; Murakami, S. Bull. Chem. Soc. Jpn. 1983, 56, 1414.
35. Kikukawa, T.; Tai, A. Chem. Lett. 1984, 1935.
36. Pommier, A.; Pons, J.-M.; Kocienski, P. J.; Wong, L. Synthesis 1994, 1294.
37. Widmer, U. Synthesis 1987, 568.
38. Hanessian, S.; Tehim, A.; Chem, P. J. Org. Chem. 1993, 58, 7768.
39. Lemieux, R. U. Can. J. Chem. 1951, 29, 415.
40. Bates, R. W.; Fernández-Moro, R.; Ley, S. V. Tetrahedron Lett. 1991, 32, 2651.