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DOI: 10.1055/s-2004-831213
Total Synthesis of the Natural Carbazoles Murrayanine and Murrayafoline A, Based on the Regioselective Diels-Alder Addition of exo-2-Oxazolidinone Dienes
Publikationsverlauf
Publikationsdatum:
02. September 2004 (online)
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Abstract
A new synthesis of the natural carbazoles Murrayanine (1) and Murrayafoline A (3) is described. The key step in the synthetic route involved the regioselective cycloaddition of the diene 4,5-dimethylene-3-phenyl-1,3-oxazolidin-2-one (4) to acrolein (6) catalyzed by Lewis acids at low temperature. Direct aromatization of the substituted cyclohexene moiety of adduct 7, and further hydrolysis of the 2-oxazolidinone ring, proved to be a more efficient strategy than the opposite synthetic sequence for the preparation of the corresponding arylphenylamines 14 and 18. Palladium-promoted cyclization of the latter furnished the desired carbazoles 1 and 3 in high overall yields.
Key words
4,5-dimethylene-2-oxazolidinone dienes - murrayanine - murrayafoline A - Diels-Alder - palladium acetate
-
1a
Chakraborty DP.Barman BK.Bose PK. Tetrahedron 1965, 21: 681 -
1b
Li W.-S.McChesney JD.El-Feraly FS. Phytochemistry 1991, 30: 343 -
1c
Bhattacharyya P.Chakraborty DP. Phytochemistry 1973, 12: 1831 -
2a
Fiebig M.Pezzuto JM.Soejarto DD.Kinghorn AD. Phytochemistry 1985, 24: 3041 -
2b
Bhattacharyya P.Chakraborty DP. In Prog. Chem. Org. Nat. Prod. Vol. 52: Herz W., Grisebach H., Kirby G. W., Tamm C., Springer Verlag; Wien: 1987. p.159 -
2c
Wu T.-S.Huang S.-C.Wu P.-L.Kuoh C.-S. Phytochemistry 1999, 52: 523 -
2d
Knölker H.-J.Reddy KR. Chem. Rev. 2002, 102: 4303 -
3a
Chakraborty DP. Planta Med. 1980, 39: 97 -
3b
Wu T.-S.Chan Y.-Y.Liou M.-J.Lin F.-W.Shi L.-S.Chen K.-T. Phytother. Res. 1998, 12: S80 -
3c
Bringmann G.Ledermann A.Holenz J.Kao M.-T.Busse U.Wu HG.François G. Planta Med. 1998, 64: 54 -
3d
Wu T.-S.Huang S.-C.Wu P.-L.Teng C.-M. Phytochemistry 1996, 43: 133 -
3e
Chakraborty A.Chowdhury BK.Bhattacharyya P. Phytochemistry 1995, 40: 295 -
4a
Knölker H.-J.Fröhner W. J. Chem. Soc., Perkin Trans. 1 1998, 173 -
4b
Knölker H.-J.Wolpert M. Tetrahedron Lett. 1997, 38: 533 -
4c
Scott TL.Söderberg BCG. Tetrahedron Lett. 2002, 43: 1621 -
4d
Majumdar KC.Das U.Kundu AK. Synth. Commun. 1998, 28: 1593 -
4e
Chakraborty A.Saha C.Podder G.Chowdhury BK.Bhattacharyya P. Phytochemistry 1995, 38: 787 -
4f
Beccalli E.Marchesini A.Pilati T. Tetrahedron 1996, 52: 3029 -
4g
Knölker H.-J.Bauermeister M.Pannek J.-B.Wolpert M. Synthesis 1995, 397 -
4h
Lee C.-Y.Lin C.-F.Lee J.-L.Chiu C.-C.Lu W.-D.Wu M.-J. J. Org. Chem. 2004, 69: 2106 -
5a
Pindur U. Chimia 1990, 44: 406 ; and references cited therein -
5b
Brenna E.Fuganti C.Serra S. Tetrahedron 1998, 54: 1585 -
5c
Choshi T.Sada T.Fujimoto H.Nagayama C.Sugino E.Hibino S. J. Org. Chem. 1997, 62: 2535 -
5d
Knölker H.-J.Schlechtingen G. J. Chem. Soc., Perkin Trans. 1 1997, 349 -
5e
Knölker H.-J.Baum E.Hopfmann T. Tetrahedron Lett. 1995, 36: 5339 -
5f
Knölker H.-J.Reddy KR. Heterocycles 2003, 60: 1049 -
5g
Scott TL.Söderberg BCG. Tetrahedron 2003, 59: 6323 -
6a
Bringmann G.Tasler S.Endress H.Peters K.Peters E.-M. Synthesis 1998, 1501 -
6b
Knölker H.-J.Bauermeister M. Tetrahedron 1993, 48: 11221 -
6c
Chakraborty DP.Chowdhury BK. J. Org. Chem. 1968, 33: 1265 - 7 For a recent synthesis of 2, see:
Knölker H.-J.Wolpert M. Tetrahedron 2003, 59: 5317 -
8a
Chowdhury BK.Chakraborty DP. Phytochemistry 1971, 10: 1967 -
8b
Chowdhury BK.Chakraborty DP. Chem. Ind. 1969, 549 -
8c
Chakraborty DP.Bhattacharyya P.Roy S.Bhattacharyya SP.Biswas AK. Phytochemistry 1978, 17: 834 - 9
Bringmann G.Ledermann A.François G. Heterocycles 1995, 40: 293 - 10
Zempoalteca A.Tamariz J. Heterocycles 2002, 57: 259 - 11
Hernández R.Sánchez JM.Gómez A.Trujillo G.Aboytes R.Zepeda G.Bates RW.Tamariz J. Heterocycles 1993, 36: 1951 - 12
Mandal AB.Gómez A.Trujillo G.Méndez F.Jiménez HA.Rosales MJ.Martínez R.Delgado F.Tamariz J. J. Org. Chem. 1997, 62: 4105 - 13
Mandal AB.Delgado F.Tamariz J. Synlett 1998, 87 - 14
Padmavathi V.Sumathi RP.Reddy KV.Reddy AS.Reddy DB. Synth. Commun. 2000, 30: 4007 - 15
Walker D.Hiebert JD. Chem. Rev. 1967, 67: 153 - 16
Åkermark B.Eberson L.Jonsson E.Pettersson E. J. Org. Chem. 1975, 40: 1365