References
<A NAME="RG22302ST-1A">1a</A>
Greenwell JF.
Benson HD.
Johnston JO.
Petrow V.
Steroids
1976,
27:
759
<A NAME="RG22302ST-1B">1b</A>
Heiman AS.
Taraporewala IB.
McLean HM.
Hong D.
Lee HJ.
J. Pharm. Sci.
1990,
79:
617
<A NAME="RG22302ST-1C">1c</A>
Manolagas SC.
Kousteni S.
Jilka RL.
Recent Prog. Horm. Res.
2002,
57:
385
<A NAME="RG22302ST-1D">1d</A>
Lednieer D.
Contraception: Chemical Control of Fertility
Marcel Dekker;
New
York:
1969.
p.88
<A NAME="RG22302ST-2">2</A>
Silberberg SD.
Magleby KL.
Science
1999,
285:
1859
See for example:
<A NAME="RG22302ST-3A">3a</A>
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
<A NAME="RG22302ST-3B">3b</A>
Zhuang ZP.
Zhou WS.
Tetrahedron
1985,
41:
3633
<A NAME="RG22302ST-3C">3c</A>
Kametani T.
Nemoto H.
Tetrahedron
1981,
37:
3
<A NAME="RG22302ST-3D">3d</A>
Kametani T.
Pure
Appl. Chem.
1979,
51:
747
<A NAME="RG22302ST-3E">3e</A>
Kametani T.
Nemoto H.
Ishikawa H.
Shiroyama K.
Fukumoto K.
J.
Am. Chem. Soc.
1976,
98:
3378
<A NAME="RG22302ST-3F">3f</A>
Oppolzer W.
Roberts DA.
Bird TGC.
Helv. Chim. Acta
1979,
62:
2017
<A NAME="RG22302ST-3G">3g</A>
Oppolzer W.
Bättig K.
Petrzilka M.
Helv.
Chim. Acta
1978,
61:
1945
<A NAME="RG22302ST-3H">3h</A>
Funk RL.
Vollhardt KPC.
J.
Am. Chem. Soc.
1979,
101:
215
<A NAME="RG22302ST-4A">4a</A>
Tietze LF.
Krahnert W.-R.
Chem.-Eur.
J.
2002,
8:
2116
<A NAME="RG22302ST-4B">4b</A>
Tietze LF.
Petersen S.
Eur. J.
Org. Chem.
2001,
1619
<A NAME="RG22302ST-4C">4c</A>
Tietze LF.
Krahnert W.-R.
Synlett
2001,
560
<A NAME="RG22302ST-4D">4d</A>
Tietze LF.
Petersen S.
Eur. J.
Org. Chem.
2000,
1827
<A NAME="RG22302ST-4E">4e</A>
Tietze LF.
Nöbel T.
Spescha M.
J. Am. Chem. Soc.
1998,
120:
8971
<A NAME="RG22302ST-4F">4f</A>
Tietze LF.
Nöbel T.
Spescha M.
Angew. Chem., Int. Ed. Engl.
1996,
35:
2259
<A NAME="RG22302ST-5A">5a</A>
Hajos ZG.
Parrish DR.
J. Org. Chem.
1974,
39:
1615
<A NAME="RG22302ST-5B">5b</A>
Eder U.
Sauer G.
Wiechert R.
Angew.
Chem., Int. Ed. Engl.
1971,
10:
496
<A NAME="RG22302ST-6A">6a</A>
Tietze LF.
Subba Rao PSV.
Synlett
1993,
291
<A NAME="RG22302ST-6B">6b</A>
Kim D.
Lee YK.
Tetrahedron Lett.
1991,
32:
6885
<A NAME="RG22302ST-6C">6c</A>
Satoh S.
Sodeoka M.
Sasai H.
Shibasaki M.
J. Org. Chem.
1991,
56:
2278
<A NAME="RG22302ST-6D">6d</A>
Hutchinson H.
Money T.
J. Chem. Soc., Chem. Commun.
1986,
288
<A NAME="RG22302ST-6E">6e</A>
Takahashi T.
Okumoto H.
Harada N.
Tsuji J.
J. Org. Chem.
1984,
49:
948
<A NAME="RG22302ST-6F">6f</A>
Takahashi T.
Okumoto H.
Tsuji J.
Tetrahedron Lett.
1984,
25:
1925
<A NAME="RG22302ST-7A">7a</A>
Groth U.
Taapken T.
Liebigs
Ann. Chem.
1994,
669
<A NAME="RG22302ST-7B">7b</A>
Groth U.
Köhler T.
Taapken T.
Tetrahedron
1991,
47:
7583
<A NAME="RG22302ST-7C">7c</A>
Daniewski AR.
Piotrowska E.
Wojciechowska W.
Liebigs Ann. Chem.
1989,
1061
<A NAME="RG22302ST-7D">7d</A>
Daniewski AR.
Kiegiel J.
Synth. Commun.
1988,
18:
115
<A NAME="RG22302ST-7E">7e</A>
Stork G.
Soccomano NA.
Tetrahedron Lett.
1987,
28:
2087
<A NAME="RG22302ST-8">8</A>
Arseniyadis S.
Rodriguez R.
Dorado MM.
Alvez RB.
Ouazzani J.
Ourisson G.
Tetrahedron
1994,
50:
8399
<A NAME="RG22302ST-9A">9a</A>
Helmchen G.
J. Organomet. Chem.
1999,
576:
203
<A NAME="RG22302ST-9B">9b</A>
Hayashi T.
J.
Organomet. Chem.
1999,
576:
195
<A NAME="RG22302ST-9C">9c</A>
Helmchen G.
Pfaltz A.
Acc. Chem. Res.
2000,
33:
336
<A NAME="RG22302ST-9D">9d</A>
Johannsen M.
Jorgensen KA.
Chem. Rev.
1998,
98:
1689
<A NAME="RG22302ST-9E">9e</A>
Tsuji J.
Mandai T.
Synthesis
1996,
1
<A NAME="RG22302ST-9F">9f</A>
Heumann A.
Reglier M.
Tetrahedron
1995,
51:
975
<A NAME="RG22302ST-9G">9g</A>
Tsuji J.
Palladium Reagents and Catalysts: Innovations in
Organic Synthesis
Wiley;
New York:
1995.
<A NAME="RG22302ST-9H">9h</A>
Trost BM.
Angew. Chem., Int. Ed. Engl.
1989,
28:
1173
<A NAME="RG22302ST-10">10</A>
Haynes RK.
Vonwiller SC.
Hambley TW.
J. Org. Chem.
1989,
54:
5162
<A NAME="RG22302ST-11">11</A>
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.
<A NAME="RG22302ST-12">12</A>
Corey EJ.
Schmidt G.
Tetrahedron Lett.
1979,
399
<A NAME="RG22302ST-13">13</A>
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.
