4
4
A. R. Maguire et al.
LETTER
(13) Thompson H.J., Jiang C., Lu J., Menta R.G., Piazza G.A.,
R-(+)-6-Fluoro-3-(4-methanesulfinylbenzyl)-2-methyl-1H-indene
a: (0.544 g, 1.80 mmol, 56%), 91% e.e., mp 101-2 °C, tr = 22.7
9
Paranka N.S., Pamukcu R. and Ahnen D.J. Cancer Res. 1997,
57, 1-6.
1
7
min, [a]D +81.2 (c = 0.98, CHCl3).
(
14) Shiff S.J., Qiao L., Tsai L.L. and Rigas B. J. Clin. Invest.
S-(-)-6-Fluoro-3-(4-methanesulfinylbenzyl)-2-methyl-1H-indene
1995, 96, 491-503.
9
b: (0.544 g, 1.80 mmol, 54%), 90% e.e., mp 101-2 °C, tr = 29.7
17
(15) Hanif R., Pittas A., Feng Y., Koutos M.I., Qiao L. Staiano
min, [a]D -83.8 (1.04, CHCl3).
Coico L., Shiff S.J. and Rigas B. Biochem. Pharmacol. 1996,
52, 237-245.
(
16) Han E.K.H., Arber N., Yamamoto H., Lim J.T.E., Delohery
T.M., Pamukcu R., Piazza G.A., Xing W.Q. and Weinstein
I.B. Cancer Res. Treat. 1998, 48, 195-203.
17) Duffy C.P., Elliott C.J., O'Connor R.A, Heenan M.M., Coyle
S., Cleary I.M., Kavanagh K., Verhaegen S., O'Loughlin C.M.
NicAmhlaoibh R. and Clynes M Eur.J. Cancer 1998, 34,
General procedure for the synthesis of Sulindac 1a, 1b and 1c.
Sulfoxide 9 (1 mmol) was placed under nitrogen and warmed to
5
0 °C. A solution of benzyltrimethylammonium hydroxide (Triton
(
B) (6.67 mmol, 40 wt.% in methanol) was added and the mixture
was stirred for 20 min. Then, a solution of glyoxylic acid (1.54
mmol, 50 wt.% in water) was added dropwise. Stirring at 50 °C was
continued for 12 hours. The mixture was cooled and the pH was
ajusted to 2 with 2 M aqueous sulfuric acid. The aqueous layer
was extracted with dichloromethane (2 ¥ 10 mL) and the combined
1260-1269.
(
(
(
(
18) Duggan D.E., Hook K.F., Risley E.A., Shen T.Y. and Arman
C.G. J. Pharmacol. Exp. Ther. 1977, 20, 8-13.
19) Swanson B.M., Boppana V.K., Richards N.J., Homs G.I.,
Davies R.O. and Huber P.B. Clin. Res. 1982, 30, 477-487.
20) Hinkley D.F. and Conn J.B. U.S. Patent, 3647858 1972;
Chem. Abstr. 1972, 76, 436.
organic layers dried (MgSO ). Flash column chromatography af-
4
forded the title compounds as yellow solids.
(+)-Sulindac 1c: 28%, mp 176-7 °C;
21) Shuman R.F., Pines S.H., Shearin W.E., Czaja R.F.,
Abramson N.L. and Tul R. J. Org. Chem. 1977, 42,
R-(+)-Sulindac 1a: 30%, 92% e.e., mp 176-7 °C, tr = 19.9 min,
17
[
a]D +50.0 (c = 0.64, methanol);
1914-1919.
S-(-)-Sulindac 1b: 30%, 89% e.e., mp 176-7 °C, tr = 15.3 min,
(
(
(
(
(
(
22) Light D.R., Waxman D.J. and Walsh C. Biochem. 1982, 21,
2490-2498.
17
[
a]D -51.6 (c = 0.56, methanol).
23) Hamman M.A., Haehner-Daniels B.D., Wrighton S.A., Rettu
A.E. and Hall S.D. Biochem. Pharmacol. 2000, 60, 7-17.
24) Fillet M., Bechet I., Schomburg G., Hubert P. and Crommen
J. J. High Resol. Chromatogr. 1996, 19,669-673.
25) Davies N.M. J. Chromatogr. Biomed Appl. 1997, 691, 229-
Acknowledgement
DCU Education Trust (SP) and BioResearch Ireland (AF) are gra-
tefully acknowledged for financial support.
261.
26) Slovakova A., Freiin Von Maltzan X., Patel B.K., Drake A.F.
and Hutt A.J. Chromatographia 1998, 48, 369-376.
27) Reviews : a) Kagan H.B. Asymmetric Oxidation of Sulfides.
In Catalytic Asymmetric Synthesis; Ojima I., Ed. VCH: New
York 1993, 203-226. b) Madesclaire M. Tetrahedron 1986,
References and Notes
(1) Brogden R.N., Heel R.C., Speight T.M. and Avery, G.S.
Drugs 1978, 16, 97-114.
(
2) Shen T.Y. and Winter C.A. in : Advances in Drug Research,
Volume 12, (Harper N.J. and Simmonds A.B., Eds.)
Academic Press, New York 1977, 89-245.
42, 5459-5495. c) Procter D.J. J. Chem. Soc., Perkin Trans. 1
1999, 835-872.
(
(
(
28) Brunel J.-M., Diter P., Duetsh M. and Kagan H.B. J. Org.
Chem. 1995, 60, 8086-8088 and references cited therein.
29) Bolm C. and Bienewald F. Angew. Chem. Int. Ed. Engl. 1995,
4, 2640-2642.
30) Reviews : a) Roberts S.M. J. Chem. Soc., Perkin Trans. 1
999, 1. b) Baird C.P. and Rayner C.M. J. Chem. Soc., Perkin
Trans. 1 1998, 1977-2003 c) Holland H.L. Chem. Rev. 1988,
8, 473-485.
(
3) Carlan S.J., O'Brien W.F., O'Leary T.D. Mastrogiannis D.
Obstet. Gynecol. 1991, 79, 223-228.
(
4) Carlan S.J., O'Brien W.F., Jones M.H. and Roth L. Obstet.
Gynecol. 1995, 85, 769-774.
3
(
(
5) Sharma Y.R. and Cotlier E. Exp. Eye Res. 1982, 35, 21-27.
6) Giardellio R.M., Hamilton S.R. and Krush A.J. N. Engl. J.
Med. 1993, 328, 1313-1316.
1
8
(
(
(
7) Heath C.W., Thun M.J., Greeberg E.R., Levin B. and Marnett
L.J. Cancer 1994, 74, 2885-2888.
(
31) a) Colonna S., Gaggero N., Carrea G. and Pasta P. Chem.
Commun. 1997, 439-440 and references cited therein. b)
Colonna S., Gaggero N., Casella L., Carrea G. and Pasta P.
Tetrahedron: Asymmetry 1992, 3, 95-106. c) van Deurzen M.
P. J., van Rantwijk T. and Sheldon R. A. Tetrahedron 1997,
8) Winde G., Schmid K.W., Schleget W., Fischer R., Osswald H.
and Bunte H. Dis. Col. Rectum 1995, 38, 813-830.
9) Pasricha P.J., Bedi A., O'Connor K., Rashid A., Akhtar A.J.
Zahurak L.M., Piantadosi S., Hamilton S.R. and Giardiello
R.M. Gastroenterology 1995, 109, 994-998.
53, 13183-13220.
(
(
32) Pasta P., Carrea G., Monzani E., Gaggero N. and Colonna S.
Biotech. Bioeng. 1999, 62, 489-493.
(
(
(
10) Pepin P., Bouchard L., Nicole P. and Castonguay A.
Carcinogenesis 1992, 13, 341-348.
33) Pines S.H. and Douglas A.W. J. Am. Chem. Soc. 1976, 99,
11) Rao C.V., Rivenson A., Simi B., Zang E., Kelloff G., Steele
V. and Reddy B.S. Cancer Res. 1995, 55, 1464-1472.
12) Thompson H.J., Briggs S., Paranka N.S., Piazza G.A., Brendel
K., Gross P.H., Sperl G.J., Pamukcu R. and Ahnen D.J. J.
Natl. Cancer Inst. 1995, 87, 1259-1260.
8119-8124.
Article Identifier:
437-2096,E;2001,0,01,0041,0044,ftx,en;L19000ST.pdf
1
Synlett 2001, No. 1, 41–44 ISSN 0936-5214 © Thieme Stuttgart · New York