Total Synthesis of (±)‐Lysergic Acid by an Intramolecular Imino‐Diels‐Alder Reaction. Preliminary communication

作者: Wolfgang Oppolzer , Eric Francotte , Kurt Bättig

DOI: 10.1002/HLCA.19810640212

关键词: StereochemistryDiels–Alder reactionIntramolecular forceChemistryTotal synthesisLysergic acidCycloadditionDieneThermal decomposition

摘要: (±)-Lysergic acid (1) has been synthesized from 4-hydroxymethyl-1-tosylindole (2) by a sequence of 9 steps. The crucial thermolysis 10 involves the in situ-generation transient diene III which undergoes an intramolecular cycloaddition to C, N-double bond at 200° and low stationary concentration III.

参考文章(28)
Lyman C. Craig, Walter A. Jacobs, Theodore Shedlovsky, R. Gordon Gould, THE ERGOT ALKALOIDS XIV. THE POSITIONS OF THE DOUBLE BOND AND THE CARBOXYL GROUP IN LYSERGIC ACID AND ITS ISOMER. THE STRUCTURE OF THE ALKALOIDS Journal of Biological Chemistry. ,vol. 125, pp. 289- 298 ,(1938)
D. RANGANATHAN, C. B. RAO, S. RANGANATHAN, A. K. MEHROTRA, R. IYENGAR, NITROETHYLENE: A STABLE, CLEAN, AND REACTIVE AGENT FOR ORGANIC SYNTHESIS ChemInform. ,vol. 11, pp. 1185- 1189 ,(1980) , 10.1002/CHIN.198029178
Kazuyoshi Seguchi, Akira Sera, Yoshinobu Otsuki, Kazuhiro Maruyama, An Investigation of theendoProduct Selectivity in the Diels-Alder Reaction Bulletin of the Chemical Society of Japan. ,vol. 48, pp. 3641- 3644 ,(1975) , 10.1246/BCSJ.48.3641
Hans Plieninger, Christina Wagner, Helga Immel, Synthese von 4-[E-4-Hydroxy-3-methyl-Δ2-butenyl]-tryptophan-[4-14C] sowie -tryptamin-[4-14C] und Einbau in Clavin-Alkaloide Justus Liebigs Annalen der Chemie. ,vol. 743, pp. 95- 111 ,(1971) , 10.1002/JLAC.19717430111
Wolfgang Oppolzer, Intramolecular [4+2] and [3+2] Cycloadditions in Organic Synthesis Angewandte Chemie International Edition in English. ,vol. 16, pp. 10- 23 ,(1977) , 10.1002/ANIE.197700101
M. Julia, F. Le Goffic, J. Igolen, M. Baillarge, Une nouvelle synthese de l'acide lysergique Tetrahedron Letters. ,vol. 10, pp. 1569- 1571 ,(1969) , 10.1016/S0040-4039(01)87946-6