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A novel and general synthetic pathway to strychnos indole alkaloids: total syntheses of (-)-tubifoline, (-)-dehydrotubifoline, and (-)-strychnine using palladium-catalyzed asymmetric allylic substitution.
J Am Chem Soc. 2003 Aug 13; 125(32):9801-7.JA

Abstract

A method of palladium-catalyzed asymmetric allylic substitution for synthesizing 2-substituted cyclohexenylamine derivatives was established. Treatment of a 2-silyloxymethylcyclohexenol derivative with ortho-bromo-N-tosylaniline in the presence of Pd(2)dba(3).CHCl(3) and (S)-BINAPO in THF afforded a cyclohexenylamine derivative with 84% ee in 80% yield. The Heck reaction was carried out to produce an indolenine derivative in good yield. Using this method, we synthesized indolenine derivative 7, which was recrystallized from EtOH to give an optically pure compound. From this compound, tetracyclic ketone 13, which should be a useful intermediate for the synthesis of indole alkaloids, could be synthesized. The total syntheses of (-)-dehydrotubifoline, (-)-tubifoline, and (-)-strychnine were achieved from 13. All ring constructions for the syntheses of these natural products were achieved using a palladium catalyst.

Authors+Show Affiliations

Mori M
Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan. mori@pharm.hokudai.ac.jp
Nakanishi M
No affiliation info available
Kajishima D
No affiliation info available
Sato Y
No affiliation info available

MeSH

Allyl CompoundsCatalysisIndole AlkaloidsIndolesPalladiumStereoisomerismStrychnine

Pub Type(s)

Journal Article

Language

eng

PubMed ID

12904045

Citation

Mori, Miwako, et al. "A Novel and General Synthetic Pathway to Strychnos Indole Alkaloids: Total Syntheses of (-)-tubifoline, (-)-dehydrotubifoline, and (-)-strychnine Using Palladium-catalyzed Asymmetric Allylic Substitution." Journal of the American Chemical Society, vol. 125, no. 32, 2003, pp. 9801-7.
Mori M, Nakanishi M, Kajishima D, et al. A novel and general synthetic pathway to strychnos indole alkaloids: total syntheses of (-)-tubifoline, (-)-dehydrotubifoline, and (-)-strychnine using palladium-catalyzed asymmetric allylic substitution. J Am Chem Soc. 2003;125(32):9801-7.
Mori, M., Nakanishi, M., Kajishima, D., & Sato, Y. (2003). A novel and general synthetic pathway to strychnos indole alkaloids: total syntheses of (-)-tubifoline, (-)-dehydrotubifoline, and (-)-strychnine using palladium-catalyzed asymmetric allylic substitution. Journal of the American Chemical Society, 125(32), 9801-7.
Mori M, et al. A Novel and General Synthetic Pathway to Strychnos Indole Alkaloids: Total Syntheses of (-)-tubifoline, (-)-dehydrotubifoline, and (-)-strychnine Using Palladium-catalyzed Asymmetric Allylic Substitution. J Am Chem Soc. 2003 Aug 13;125(32):9801-7. PubMed PMID: 12904045.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - A novel and general synthetic pathway to strychnos indole alkaloids: total syntheses of (-)-tubifoline, (-)-dehydrotubifoline, and (-)-strychnine using palladium-catalyzed asymmetric allylic substitution. AU - Mori,Miwako, AU - Nakanishi,Masato, AU - Kajishima,Daisuke, AU - Sato,Yoshihiro, PY - 2003/8/9/pubmed PY - 2003/12/3/medline PY - 2003/8/9/entrez SP - 9801 EP - 7 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 125 IS - 32 N2 - A method of palladium-catalyzed asymmetric allylic substitution for synthesizing 2-substituted cyclohexenylamine derivatives was established. Treatment of a 2-silyloxymethylcyclohexenol derivative with ortho-bromo-N-tosylaniline in the presence of Pd(2)dba(3).CHCl(3) and (S)-BINAPO in THF afforded a cyclohexenylamine derivative with 84% ee in 80% yield. The Heck reaction was carried out to produce an indolenine derivative in good yield. Using this method, we synthesized indolenine derivative 7, which was recrystallized from EtOH to give an optically pure compound. From this compound, tetracyclic ketone 13, which should be a useful intermediate for the synthesis of indole alkaloids, could be synthesized. The total syntheses of (-)-dehydrotubifoline, (-)-tubifoline, and (-)-strychnine were achieved from 13. All ring constructions for the syntheses of these natural products were achieved using a palladium catalyst. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/12904045/A_novel_and_general_synthetic_pathway_to_strychnos_indole_alkaloids:_total_syntheses_of_____tubifoline_____dehydrotubifoline_and_____strychnine_using_palladium_catalyzed_asymmetric_allylic_substitution_ DB - PRIME DP - Unbound Medicine ER -