LETTER
Strategy for the Convergent Synthesis of 1,3,5,…-Polyols
2909
(11) Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43,
2923.
(26) Hosaka, M.; Hayakawa, H.; Miyashita, M. J. Chem. Soc.,
Perkin Trans. 1 2000, 4227.
(12) Enantioselective AD of achiral a,b-unsaturated ketones:
(a) Becker, H.; Soler, M. A.; Sharpless, K. B. Tetrahedron
1995, 51, 1345. (b) Takikawa, H.; Shimbo, K.-i.; Mori, K.
Liebigs Ann./Recl. 1997, 821. (c) Yokoyama, Y.; Mori, K.
Liebigs Ann./Recl. 1997, 849. (d) List, B.; Shabat, D.;
Barbas, C. F. III; Lerner, R. A. Chem.–Eur. J. 1998, 4, 881.
(e) Giner, J.-L. Tetrahedron Lett. 1998, 39, 2479.
(f) Shabat, D.; List, B.; Lerner, R. A.; Barbas, C. F. III
Tetrahedron Lett. 1999, 40, 1437. (g) Toshima, H.;
Aramaki, H.; Ichihara, A. Tetrahedron Lett. 1999, 40, 3587.
(h) Schuricht, U.; Endler, K.; Hennig, L.; Findeisen, M.;
Welzel, P. J. Prakt. Chem. 2000, 342, 761. (i) Rieder, C.;
Jaun, B.; Arigoni, D. Helv. Chim. Acta 2000, 83, 2504.
(j) Naoki, Y.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002,
67, 2556. (k) Cox, R. J.; de Andres-Gomez, A.; Godfrey, C.
R. A. Org. Biomol. Chem. 2003, 1, 3173. (l) Kumar, D. N.;
Rao, B. V. Tetrahedron Lett. 2004, 45, 2227.
(13) Diastereoselective AD of g-chiral a,b-unsaturated ketones:
(a) Carreira, E. J.; DuBois, J. J. Am. Chem. Soc. 1995, 117,
8106. (b) Cid, M. B.; Pattenden, G. Synlett 1998, 540.
(c) Ishiyama, H.; Takemura, T.; Tsuda, M.; Kobayashi, J.-i.
J. Chem. Soc., Perkin Trans. 1 1999, 1163. (d) Ohi, K.;
Nishiyama, S. Synlett 1999, 573. (e) Lee, D.-H.; Rho, M.-D.
Tetrahedron Lett. 2000, 41, 2573.
(14) Diastereoselective AD of d- and b¢-chiral a,b-unsaturated
ketones: Nicolaou, K. C.; Li, Y.; Sugita, K.; Monenschein,
H.; Guntupalli, P.; Mitchell, H. J.; Fylaktakidou, K. C.;
Vourloulis, D.; Giannakakou, P.; O’Brate, A. J. Am. Chem.
Soc. 2003, 125, 15443.
(15) Diastereoselective AD of b¢-chiral a,b-unsaturated ketones:
(a) Schuppan, J.; Ziemer, B.; Koert, U. Tetrahedron Lett.
2000, 41, 621. (b) Trost, B. M.; Harrington, P. E. J. Am.
Chem. Soc. 2004, 126, 5028. (c) Trost, B. M.; Wrobelski, S.
T.; Chisholm, J. D.; Harrington, P. E.; Jung, M. J. Am. Chem.
Soc. 2005, 127, 13589.
(27) Rho, H.-S. Synth. Commun. 1997, 27, 3887.
(28) (a) (4R)-4-Hydroxy-2-octanone (11a).
At –78 °C a solution of SmI2 (0.1 M in THF, 42 mL, 4.2
mmol, 2.1 equiv) was added dropwise to a stirred solution of
acetonide aS,bR-12a (0.40 g, 2.0 mmol) in THF (12 mL) and
MeOH (6 mL). After 15 min the reaction mixture was
gradually warmed to r.t. (within 30 min) and aq HCl (1 M,
4.2 mL) was added. After evaporating volatile material in
vacuo the residue was diluted with H2O (10 mL) and
extracted with t-BuOMe (3 ꢀ 15 mL). The combined organic
extracts were washed with sat. aq NaHCO3 (10 mL) and
brine (8 mL) and dried over MgSO4. Removal of the solvent
in vacuo and purification of the residue by flash
chromatography on silica gel11 (column filling 1.5 cm ꢀ 15
cm, cyclohexane–EtOAc 4:1, 4 mL fractions) afforded the
title compound (fractions 20–39, 0.186 g, 65%) as a
colorless oil. 1H NMR (400 MHz, MHz, TMS internal
standard in CDCl3): d = 0.91 (t, J8,7 = 7.1 Hz, 8-H3), 1.29–
1.54 (m, 5-H2, 6-H2, 7-H2), 2.18 (s, 1-H3), AB signal
(dA = 2.53, dB = 2.62, JAB = 17.7 Hz, A part in addition split
by JA,4 = 9.0 Hz, B part in addition split by JB,4 = 2.9 Hz, 3-
H2), 2.94 (br s, 4-OH), 4.03 (mc, 4-H). [a]D20 –31.50 (c 0.20,
CHCl3). IR (CDCl3): d = 3565, 2960, 2935, 2875, 2860,
1705, 1470, 1460, 1415, 1385, 1365, 1315, 1275, 1165, 1060
cm–1. Anal. Calcd for C8H16O2 (144.2): C, 66.63; H, 11.18.
Found: C, 66.74; H, 10.97. (b) Enantiomer S-11a was
prepared by an organocatalytic aldol addition (86% ee, 12%
yield). See: Tang, Z.; Jiang, F.; Yu, L.-T.; Cui, X.; Gong, L.-
Z.; Mi, A.-Q.; Jiang, Y.-Z.; Wu, Y.-D. J. Am. Chem. Soc.
2003, 125, 5262.
(29) Borinylated b-hydroxyketone and NaBH4: (a) Narasaka, K.;
Pai, F.-C. Chem. Lett. 1980, 1415. (b) Narasaka, K.; Pai,
F.-C. Tetrahedron 1984, 40, 2233. (c) Chen, K.-M.;
Hardtmann, G. E.; Prasad, K.; Repic, O.; Shapiro, M. J.
Tetrahedron Lett. 1987, 28, 155. (d) Chen, K.-M.;
Gunderson, K. G.; Hardtmann, G. E.; Prasad, K.; Repic, O.;
Shapiro, M. J. Chem. Lett. 1987, 1923.
(30) BCl3-complexed b-hydroxyketone and tetraalkylammonium
boronate: Sarko, C. S.; Collibee, S. E.; Knorr, A. R.;
DiMare, M. J. Org. Chem. 1996, 61, 868.
(16) Review: Kagan, H. B. Tetrahedron 2003, 59, 10351.
(17) Confer ref. 18a for a different rationalization.
(18) (a) Molander, G. H.; Hahn, G. J. Org. Chem. 1986, 51,
1135. (b) Similarly an Oa–SiMe2t-Bu bond was cleaved off
a ketone by: Abad, A.; Agulló, C.; Arnó, M.; Cuñat, A. C.;
García, M. T.; Zaragozá, R. J. J. Org. Chem. 1996, 61, 5916.
(19) (a) Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc.
1997, 119, 4557. (b) Mori, Y.; Yaegashi, K.; Furukawa, H.
J. Org. Chem. 1998, 63, 6200. (c) Voight, E. A.; Seradj, H.;
Roethle, P.; Burke, S. D. Org. Lett. 2004, 6, 4045.
(20) In lactones, oxygen-containing a-substituents including OH
groups can be removed by SmI2 in THF–HMPA, too:
Hanessian, S.; Girard, C.; Chiara, J. L. Tetrahedron Lett.
1992, 33, 573.
(31) Reduction with DIBAL-H: Kiyooka, S.; Kuroda, H.;
Shimasaki, Y. Tetrahedron Lett. 1986, 27, 3009.
(32) Reduction with catecholborane: Evans, D. A.; Hoveyda, A.
H. J. Org. Chem. 1990, 55, 5190.
(33) (a) Reduction with Zn(BH4)2: Kashihara, H.; Suemune, H.;
Fujimoto, K.; Sakai, K. Chem. Pharm. Bull. 1989, 37, 2610;
in Et2O. (b) Dakin, L. A.; Panek, J. S. Org. Lett. 2003, 5,
3995; in CH2Cl2.
(34) Reduction with tetraalkylammonium triacetoxyboro-
hydride: (a) Evans, D. A.; Chapman, K. T. Tetrahedron Lett.
1986, 27, 5939. (b) Evans, D. A.; Chapman, K. T.; Carreira,
E. M. J. Am. Chem. Soc. 1988, 110, 3560. (c) See also with
sodium triacetoxyborohydride: Roeyeke, Y.; Keller, M.;
Kluge, H.; Grabley, S.; Hammann, P. Tetrahedron 1991, 47,
3335.
(35) Intramolecular hydrosilylation: (a) Anwar, S.; Davis, A. P.
J. Chem. Soc., Chem. Commun. 1986, 831. (b) Anwar, S.;
Davis, A. P. Tetrahedron 1988, 44, 3761.
(36) (a) Reduction with SmI2 and an aldehyde: Evans, D. A.;
Hoveyda, A. H. J. Am. Chem. Soc. 1990, 112, 6447.
Related Tishchenko reductions: (b) Schneider, C.; Klapa,
K.; Hansch, M. Synlett 2005, 91 and literature cited therein.
(37) LiClO4-complexed b-hydroxyketone and amine-complexed
BH3: Narayana, C.; Reddy, M. R.; Hair, M.; Kabalka, G. W.
Tetrahedron Lett. 1997, 38, 7705.
(21) Holton, R. A.; Somoza, C.; Chai, K.-B. Tetrahedron Lett.
1994, 35, 1665.
(22) (a) Py, S.; Khuong-Huu, F. Tetrahedron Lett. 1995, 36,
1661. (b) Georg, G. I.; Cheruvallath, Z. S.; Vander Velde, D.
G.; Himes, R. H. Tetrahedron Lett. 1995, 36, 1783.
(c) Georg, G. I.; Harriman, G. C. B.; Datta, A.; Ali, S.;
Cheruvallath, Z. S.; Vander Velde, D. G.; Himes, R. H. J.
Org. Chem. 1998, 63, 8926.
(23) Molander, G. H.; Hahn, G. J. Org. Chem. 1986, 51, 2596.
(24) White, D. J.; Nolen, E. G. Jr.; Miller, C. H. J. Org. Chem.
1986, 51, 1150.
(25) (a) Smith, A. B. III; Dunlap, N. K.; Sulikowski, G. A.
Tetrahedron Lett. 1988, 29, 439. (b) Kim, D.; Min, J.; Ahn,
S. K.; Lee, H. W.; Choi, N. S.; Moon, S. K. Chem. Pharm.
Bull. 2004, 52, 447.
Synlett 2005, No. 19, 2905–2910 © Thieme Stuttgart · New York