Abstract
The synthesis of optically pure (-)-isosteviol derivatives with a keto function shifted to position 15 and its insertive esterification are described.
Key words
terpenoids - chiral pool - esters - carbocycles - rearrangements
References
1
Starraat AN.
Kirby CW.
Pocs R.
Brandle JE.
Phytochemistry
2002,
59:
367
2a
Mosettig E.
Nes WR.
J. Org. Chem.
1955,
20:
884
2b
Mosettig E.
Beglinger U.
Dolder F.
Lichti H.
Quitt P.
Waters JA.
J. Am. Chem. Soc.
1963,
85:
2305
3
Alfonsov VA.
Bakaleynik GA.
Gubaidullin AT.
Kataev VE.
Kovyljaeva GI.
Konovalov AI.
Litvinov IA.
Strobykina IYu.
Andreeva OV.
Korochkina MG.
Mendeleev Commun.
1999,
6:
227
4
Bomkamp M.
Artiukhov A.
Kataeva O.
Waldvogel SR.
Synthesis
2007,
1107
5a
Waldvogel SR.
Fröhlich R.
Schalley CA.
Angew. Chem. Int. Ed.
2000,
39:
2472
5b
Bomkamp M.
Siering C.
Landrock K.
Stephan H.
Fröhlich R.
Waldvogel SR.
Chem. Eur. J.
2007,
13:
3724
6a
Schopohl MC.
Siering C.
Kataeva O.
Waldvogel SR.
Angew. Chem. Int. Ed.
2003,
42:
2620
6b
Schophol MC.
Faust A.
Mirk D.
Fröhlich R.
Kataeva O.
Waldvogel SR.
Eur. J. Org. Chem.
2005,
2987
7
Fabris F.
Zambrini L.
Rosso E.
De Lucchi O.
Eur. J. Org. Chem.
2004,
15:
3313
8
Coates MC.
J. Org. Chem.
1987,
52:
2065
9
Rabjohn N.
Org. React.
1976,
24:
261
10
Cram DJ.
Sahyun MRV.
J. Am. Chem. Soc.
1962,
84:
1734
11
Caglioti L.
Tetrahedron
1966,
22:
487
12
Frey B.
Schnaubelt J.
Reißig H.-U.
Eur. J. Org. Chem.
1999,
1385
13a
Waldvogel SR.
Mirk D.
Tetrahedron Lett.
2000,
41:
4769
13b
Waldvogel SR.
Mirk D.
Herbrüggen J.
GDCh-Monographie
2001,
23:
233
14 Tested reaction conditions for the synthesis of 8 : (+)-Methyl-ent -15-oxobeyeran-19-oate (6 ) was dissolved in toluene, chlorobenzene or 1,2-dichlorobenzene and, after addition of catechol and a catalytic amount of a Brønsted acid, the mixture was heated under reflux applying a Dean-Stark trap. Even under very harsh conditions such as TsOH in boiling 1,2-dichlorobenzene (180 °C) or TfOH in boiling toluene, no product formation was observed.
15
Alfonsov VA.
Andreeva OV.
Bakaleynik GA.
Beskrovny DV.
Kataev VE.
Kovyljaeva GI.
Litvinov IA.
Militsina OI.
Strobykina IYu.
Mendeleev Commun.
2003,
13:
234
16
Alfonsov VA.
Andreeva OV.
Bakaleynik GA.
Beskrovny DV.
Gubaidullin AT.
Kataev VE.
Kovyljaeva GI.
Konovalov AI.
Korochkina MG.
Latypov ShK.
Litvinov IA.
Musin RZ.
Strobykina IYu.
Russ. J. Gen. Chem.
2003,
73:
1119
17
Nishio M.
Hirota M.
Umezawa Y.
The CH/π Interaction: Evidence, Nature and Consequences
Wiley-VCH;
New York:
1998.
18
Otwinowski Z.
Minor W.
Methods Enzymol.
1997,
276:
307
19
Otwinowski Z.
Borek D.
Majewski W.
Minor W.
Acta Crystallogr. A
2003,
59:
228
20
Sheldrick GM.
Acta Cryst.
1990,
A46:
467
21 G. M. Sheldrick; Universität Göttingen, 1997 .