November 1998
SYNLETT
1225
13 Synthesis of sulfones 3 and 4 will be published elsewhere.
1) CSA, PhH
reflux
OMe
MeO OMe
R
14 In comparative experiments, the reaction of the anion derived
from 4-desmethylsulfone analogue of 3 with benzaldehyde or 3-
phenylpropionaldehyde led to the expected condensation products
in 80-85% yields.
R
O
O
2) CH2N2, Et2O
60-73%
OMe
OMe
9a-c
8a-c
15 This chiral aldehyde was synthesized by ozonolysis of the
corresponding Hoppe's homoaldolisation vinylcarbamate adduct
prepared for other synthetic work in our laboratories (unpublished
results), see Hoppe, D.; Hanko, R.; Brönneke, A.; Lichtenberg, F.;
van Hülsen, E. Chem. Ber. 1985, 118, 2822.
Scheme 5
Acknowledgments: The CNRS (URA 1308) and the Ecole
Polytechnique are thanked for financial support.
16 Hydroxysulfones 6a,b were obtained as 3:1 and 1:1
diastereomeric mixtures respectively whereas the corresponding
lactones 7a,b were obtained as 2:1 and 6:5 mixtures. Interestingly,
lactone 7c only exists as a ca. 2:1 diastereomeric mixture which
probably indicates an efficient diastereoselective Felkin-Ahn
controlled condensation.
References and Notes
1
Werner, G.; Hagenmaier, H.; Albert, K.; Kohlshorn, H.; Drautz,
H. Tetrahedron Lett. 1983, 24, 5193; Werner, G.; Hagenmaier, H.;
Drautz, H.; Baumgartner, A.; Zähner, H. J. Antibiot. 1984, 37,
110. For their structure elucidation : Corey, E. J.; Ponder, J. W.
Tetrahedron Lett. 1984, 25, 4325; Baker, G. H.; Brown, P. J.;
Dorgan, R. J. J.; Everett J. R.; Ley, S. V.; Slawin, A. M. Z.;
Williams, D. J. Tetrahedron Lett. 1987, 28, 5565.
17 Obtention of δ-lactones after condensation of dianions derived
from 4-(phenylsulfonyl)butanoic acid on aldehydes followed by
acidic work-up has been precedented whereas the course of the
subsequent Na/Hg reductive elimination step has been shown to
involve an initial methanolysis of the lactone function, a fact
which has not been observed in our examples : Thompson, C. M.;
Frick, J. A. J. Org. Chem., 1989, 54, 890.
2
3
4
5
a) Bowman, E. J.; Siebers, A.; Altendorf, K. Proc. Natl. Acad. Sci.
1988, 85, 7972. b) Bindseil, K. U.; Zeeck, A. Liebigs Ann. Chem.,
1994, 305.
Kinashi, H.; Someno, K.; Sakaguchi, K.; Higashijima, T.;
Miyazawa, T. Tetrahedron Lett. 1981, 22, 3857; idem 3861;
Kinashi H.; Someno K.; Sakaguchi K. J. Antibiot. 1984, 37, 1333.
18 Keck, G. E.; Savin, K. A.; Weglarz, M. A. J. Org. Chem. 1995,
60, 3194 and references cited therein.
Seto H.; Akao H.; Furihata K.; Otake N. Tetrahedron Lett. 1982,
23, 2667; Seto, H.; Tajima, I.; Akao, H.; Furihata, K.; Otake, N. J.
Antibiot. 1984, 37, 610.
19 Inanaga, J.; Ishikawa, M.; Yamaguchi, M. Chem. Lett. 1987,
1485; Ujikawa, O.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett.
1989, 30, 2837. Ihara, M.; Suzuki, S.; Taniguchi, S.; Tokunaga,
Y.; Fukumoto, K. Synlett 1994, 859. Shabangi, M. S.; Flowers II,
R. A. Tetrahedron Lett. 1997, 38, 1137.
Total syntheses : (a) Evans, D. A.; Calter, M. A. Tetrahedron Lett.
1993, 34, 6871; (b) Toshima, K.; Jyojima, T.; Yamaguchi, H.;
Murase, H.; Yoshida, T.; Matsumura, S.; Nakata, M. Tetrahedron
Lett. 1996, 37, 1069. (c) Toshima, K.; Yamaguchi, H.; Jyojima,
T.; Noguchi, Y.; Nakata, M.; Matsumura, S Tetrahedron Lett.
1996, 37, 1073. d) Toshima, K.; Jyojima, T.; Noguchi, Y.;
Yoshida, T.; Murase, M.; Nakata, M.; Matsumura, S. J. Org.
Chem. 1997, 62, 3271. Partial syntheses : e) Roush, W. R.;
Bannister, T. D. Tetrahedron Lett. 1992, 33, 3587. f) Roush, W.
R.; Bannister, T. D.; Wendt, M. D. Tetrahedron Lett. 1993, 34,
8387; g) Paterson, I.; Bower, S.; McLeod, M.D. Tetrahedron Lett.
1995, 36, 175. h) Hanessian, S.; Wang, W.; Gai, Y.; Olivier, E. J.
Am. Chem. Soc, 1997, 119, 10034.
20 Typical procedures for reductive elimination reactions:
Na/Hg : To a stirred suspension of Na/Hg 6% in 4 ml of dry
MeOH at -20 °C (570 mg, 1.5 mmol, 5 equiv) was slowly added
via cannula alkoxysulfone in 1.5 ml of dry MeOH plus 0.5 ml
rinse (0.3 mmol, 1 equiv). The resulting suspension was stirred at
this temperature until no starting material remained
O and
(approximately 6 hours) then partitioned between Et2
aqueous buffer (pH 7). The layers were separated, and the aqueous
phase was extracted 3 times with Et2O. The combined organic
layers were washed twice with brine, dried over MgSO4 and
concentrated in vacuo to give after flash chromatography on silica
gel (petroleum ether/AcOEt 95/5 to 9/1) the desired alkene. In the
cases where carboxylates were formed, the combined organic
phases were washed with dilute aqueous HCl (2%) and the crude
extract was treated with a solution of CH2N2 in Et2O before
chromatography.
SmI2/HMPA : to a stirred solution of SmI2 (freshly prepared from
Sm powder and I2 in THF (0.1 M, 25 ml, 2.5 mmol, 5 eq) at room
temperature was slowly added HMPA (130 µl, 7.5 mmol, 15
equiv), then after stirring 15 min, a solution of alkoxysulfone (0.5
mmol, 1 eq) in 5 ml of THF. The reaction mixture was stirred for
10 min at the same temperature, then diluted with Et2O and
washed with 2% aqueous HCl, saturated aqueous NaHCO3, brine,
and, after decantation, dried over MgSO4. Evaporation of the
6
7
Kishi, Y.; Johnson, M.R. Tetrahedron Lett. 1979, 4347.
Makino, K.; Kimura, K.-I.; Nakajima, N.; Hashimoto, S.-I.;
Yonemitsu, O. Tetrahedron Lett. 1996, 37, 9073; Makino, K.;
Nakajima, N.; Hashimoto, S.-I.; Yonemitsu, O. idem, 9077.
8
9
McCann, E. E.; Janes, G.; Ortsey, C.; Wood, J. L. Tetrahedron
Lett. 1997, 38, 303.
Paterson, I.; McLeod, M. D. Tetrahedron Lett. 1997, 38, 4183.
10 Julia, M.; Paris, J. M.; Tetrahedron Lett., 1973, 4833; Lythgoe,
B.; Waterhouse, I. Tetrahedron lett. 1977, 4223. For
a
monography: Simpkins, N. S. "Sulphones in Organic Chemistry"
in Tetrahedron Organic Chemistry Series, Baldwin, J. E. and
Magnus, P. D. Eds, Pergamon Press, Oxford, 1993.
11 See for example, Keck, G. E.; Kachensky, D. F.; Enholm, E. J. J.
Org. Chem. 1985, 50, 4317. Hirama, M.; Nakamine, T.; Itô, S.
Tetrahedron Lett. 1988, 29, 1197.
solvent gave
a residue, which was subjected to flash
chromatography on silica gel (petroleum ether/AcOEt 95/5 to 9/1)
to afford the desired alkene. In the case where carboxylates are
formed, washing with aqueous NaHCO3 was avoided and the
crude extract was treated with a solution of CH2N2 in Et2O as
above.
12 a) Kende, A.S.; liu, K.; Kaldor, I.; Dorey, G.; Koch, K. J. Am.
Chem. Soc, 1995, 117, 8258. b) Markó, I. E.; Murphy, F.; Solan,
S. Tetrahedron Lett. 1996, 37, 2089.