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DOI: 10.1055/s-2003-36225
Stereoselective Synthesis of New Enantiopure Building Blocks for the Preparation of Steroids
Publication History
Publication Date:
18 December 2002 (online)
Abstract
The enantiopure α,β-unsaturated ketone 4 was synthesised from indanone 2 by a palladium-catalysed hydrogenolysis of allylic formate 10 followed by deprotection of TBS-ether 11 and oxidation with MnO2.
Key words
epoxidation - indane - oxidation - palladium - steroids
-
1a
Greenwell JF.Benson HD.Johnston JO.Petrow V. Steroids 1976, 27: 759 -
1b
Heiman AS.Taraporewala IB.McLean HM.Hong D.Lee HJ. J. Pharm. Sci. 1990, 79: 617 -
1c
Manolagas SC.Kousteni S.Jilka RL. Recent Prog. Horm. Res. 2002, 57: 385 -
1d
Lednieer D. Contraception: Chemical Control of Fertility Marcel Dekker; New York: 1969. p.88 - 2
Silberberg SD.Magleby KL. Science 1999, 285: 1859 - See for example:
-
3a
Quinkert G.Del Grosso M.Döring A.Döring W.Schenkel RI.Bauch M.Dambacher GT.Bats JW.Zimmermann G.Dürner G. Helv. Chim. Acta 1995, 78: 1345 -
3b
Zhuang ZP.Zhou WS. Tetrahedron 1985, 41: 3633 -
3c
Kametani T.Nemoto H. Tetrahedron 1981, 37: 3 -
3d
Kametani T. Pure Appl. Chem. 1979, 51: 747 -
3e
Kametani T.Nemoto H.Ishikawa H.Shiroyama K.Fukumoto K. J. Am. Chem. Soc. 1976, 98: 3378 -
3f
Oppolzer W.Roberts DA.Bird TGC. Helv. Chim. Acta 1979, 62: 2017 -
3g
Oppolzer W.Bättig K.Petrzilka M. Helv. Chim. Acta 1978, 61: 1945 -
3h
Funk RL.Vollhardt KPC. J. Am. Chem. Soc. 1979, 101: 215 -
4a
Tietze LF.Krahnert W.-R. Chem.-Eur. J. 2002, 8: 2116 -
4b
Tietze LF.Petersen S. Eur. J. Org. Chem. 2001, 1619 -
4c
Tietze LF.Krahnert W.-R. Synlett 2001, 560 -
4d
Tietze LF.Petersen S. Eur. J. Org. Chem. 2000, 1827 -
4e
Tietze LF.Nöbel T.Spescha M. J. Am. Chem. Soc. 1998, 120: 8971 -
4f
Tietze LF.Nöbel T.Spescha M. Angew. Chem., Int. Ed. Engl. 1996, 35: 2259 -
5a
Hajos ZG.Parrish DR. J. Org. Chem. 1974, 39: 1615 -
5b
Eder U.Sauer G.Wiechert R. Angew. Chem., Int. Ed. Engl. 1971, 10: 496 -
6a
Tietze LF.Subba Rao PSV. Synlett 1993, 291 -
6b
Kim D.Lee YK. Tetrahedron Lett. 1991, 32: 6885 -
6c
Satoh S.Sodeoka M.Sasai H.Shibasaki M. J. Org. Chem. 1991, 56: 2278 -
6d
Hutchinson H.Money T. J. Chem. Soc., Chem. Commun. 1986, 288 -
6e
Takahashi T.Okumoto H.Harada N.Tsuji J. J. Org. Chem. 1984, 49: 948 -
6f
Takahashi T.Okumoto H.Tsuji J. Tetrahedron Lett. 1984, 25: 1925 -
7a
Groth U.Taapken T. Liebigs Ann. Chem. 1994, 669 -
7b
Groth U.Köhler T.Taapken T. Tetrahedron 1991, 47: 7583 -
7c
Daniewski AR.Piotrowska E.Wojciechowska W. Liebigs Ann. Chem. 1989, 1061 -
7d
Daniewski AR.Kiegiel J. Synth. Commun. 1988, 18: 115 -
7e
Stork G.Soccomano NA. Tetrahedron Lett. 1987, 28: 2087 - 8
Arseniyadis S.Rodriguez R.Dorado MM.Alvez RB.Ouazzani J.Ourisson G. Tetrahedron 1994, 50: 8399 -
9a
Helmchen G. J. Organomet. Chem. 1999, 576: 203 -
9b
Hayashi T. J. Organomet. Chem. 1999, 576: 195 -
9c
Helmchen G.Pfaltz A. Acc. Chem. Res. 2000, 33: 336 -
9d
Johannsen M.Jorgensen KA. Chem. Rev. 1998, 98: 1689 -
9e
Tsuji J.Mandai T. Synthesis 1996, 1 -
9f
Heumann A.Reglier M. Tetrahedron 1995, 51: 975 -
9g
Tsuji J. Palladium Reagents and Catalysts: Innovations in Organic Synthesis Wiley; New York: 1995. -
9h
Trost BM. Angew. Chem., Int. Ed. Engl. 1989, 28: 1173 - 10
Haynes RK.Vonwiller SC.Hambley TW. J. Org. Chem. 1989, 54: 5162 - 12
Corey EJ.Schmidt G. Tetrahedron Lett. 1979, 399
References
Experimental Details for the Tsuji-Trost-Reaction: To a degassed solution of 10 (1.70 g, 4.31 mmol)in dioxane (15 mL) were added Pd(OAc)2 (10 mg, 0.045 mmol) and P(n-Bu)3 (0.040 mL, 0.18 mmol). The reaction mixture was stirred for 45 min at 90 °C. Then the reaction mixture was allowed to attain r.t. and diluted with Et2O and H2O. The organic layer was washed with brine, dried over Na2SO4, and concentrated in vacuo. Purification by silica gel column chromatography(pentane) afforded 1.06 g (70%) of 11 and 12 (4:1 mixture) as colourless oil, which was used for the next step without separation. Separation of 12 is possible using pentane/ethyl acetate (100:1), but easier at a later stage.
13
Compound 3:
Rf = 0.11 (pentane/ethyl
acetate 10:1), [α]D
20 = +56.0
(c 1, CHCl3). 1H
NMR (300 MHz, CDCl3): δ = 0.76
(s, 3 H), 1.14 (s, 9 H), 1.14-1.69 (m, 5 H), 1.86-2.05
(m, 1 H), 2.10-2.20 (m, 1 H), 2.32 (dd, J = 11.9,
7.0 Hz, 1 H), 3.54 (dd, J = 9.0,
6.8 Hz, 1 H), 4.41 (mc, 1 H), 5.60 (dt, J = 9.7,
2.6 Hz, 1 H), 5.73 (dt, J = 9.7,
1.5 Hz, 1 H). 13C NMR (50.3 MHz, CDCl3): δ = 10.93,
23.72, 27.98, 30.32, 43.08, 44.08, 44.76, 67.29, 71.65, 78.27, 128.80,
129.60.
Compound 4: Rf = 0.21
(pentane/ethyl acetate 10:1), [α]D
20 = +24.3
(c 1, CHCl3). 1H
NMR (300 MHz, CDCl3): δ = 0.83
(d, J = 1.0
Hz, 3 H), 1.14 (s, 9 H), 1.53-1.69 (m, 2 H), 1.78-1.90
(m, 1 H), 2.01-2.14 (m, 1 H), 2.14 (dd, J = 16.2,
0.9 Hz, 1 H), 2.50-2.61 (m, 1 H), 2.60 (d, J = 16.2 Hz,
1 H), 3.71 (dd, J = 8.9,
7.0 Hz, 1 H), 5.96 (ddd, J = 9.9, 3.1,
0.8 Hz, 1 H), 6.81 (dd, J = 9.9,
2.3 Hz, 1 H). 13C NMR (50.3 MHz, CDCl3): δ = 11.95,
23.88, 28.54, 31.30, 44.32, 46.76, 52.08, 72.63, 78.70, 129.60,
149.80, 200.60.