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Synthesis 2004(7): 1093-1101  
DOI: 10.1055/s-2004-816009
PAPER
© Georg Thieme Verlag Stuttgart · New York

Stereoselective Synthesis of Aporphine Alkaloids Using a Hypervalent Iodine­(III) Reagent-Promoted Oxidative Nonphenolic Biaryl Coupling Reaction­. Total Synthesis of (S)-(+)-Glaucine

Eneritz Anakabe, Luisa Carrillo, Dolores Badía*, Jose L. Vicario, Maite Villegas
Departamento de Química Orgánica II, Facultad de Ciencia y Tecnología, Universidad del País Vasco/Euskal Herriko Unibertsitatea, P.O. Box 644, 48080 Bilbao, Spain
Fax: +34(94)6012748; e-Mail: qopbaurm@lg.ehu.es.;
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Publication History

Received 18 December 2003
Publication Date:
15 March 2004 (online)

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Abstract

The aporphine alkaloid (+)-glaucine (8a) and two other analogues 8b,c have been synthesized in good yield and high ee from the appropriate 1,2-diarylethylamine derivatives, which were in turn prepared using (S)-(+)-phenylglycinol as chiral support. Next, a sequence of simple transformations: N-alkylation with bromoacetaldehyde diethyl acetal, N-methylation, Pommeranz-Fritsch cyclization, and ionic hydrogenation led to the key intermediate, optically active, 1-benzyltetrahydroisoquinolines 7a-c. The final C-ring closure step was performed by C-C biaryl bond formation by an hypervalent iodine(III) reagent promoted oxidative coupling, affording the target heterocycles 8a-c in good yields and with no racemization at the formerly created stereogenic center.

Key words

alkaloids - amino alcohols - asymmetric synthesis - chiral auxiliaries - iodine