Total syntheses of the monoterpene indole alkaloids (±)- alstilobanine A and e and (±)-angustilodine

Yiqing Feng, Max M. Majireck, Steven M. Weinreb

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

A synthetic strategy has been developed culminating in stereoselective total syntheses of the small class of unusual monoterpenoid indole alkaloids exemplified by alstilobanines A (3) and E (2) and angustilodine (1). A pivotal step includes a novel intermolecular Michael-type addition of an indole ester dianion to a piperidine-derived nitrosoalkene to form the C15, C16 bond of the alkaloids. In addition, an application of the Romo protocol for effecting a stereoselective intramolecular nucleophile-assisted aldol-lactonization was employed, leading to a β-lactone incorporating the requisite cis-fused 2-azadecalin moiety and also setting the C15, C19, C20 relative stereochemistry of the metabolites. It was then possible to stereoselectively effect an aldolization of a dianion derived from this indole ester β-lactone intermediate with formaldehyde to introduce the requisite C16 hydroxymethyl group. Further manipulations of the system ultimately led to the three alkaloids in racemic form.

Original languageEnglish (US)
Pages (from-to)7-24
Number of pages18
JournalJournal of Organic Chemistry
Volume79
Issue number1
DOIs
StatePublished - Jan 3 2014

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Indole Alkaloids
Monoterpenes
Lactones
Alkaloids
Esters
Secologanin Tryptamine Alkaloids
Nucleophiles
Stereochemistry
Metabolites
Formaldehyde
indole
alstilobanine A
angustilodine
piperidine
3-hydroxybutanal

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Feng, Yiqing ; Majireck, Max M. ; Weinreb, Steven M. / Total syntheses of the monoterpene indole alkaloids (±)- alstilobanine A and e and (±)-angustilodine. In: Journal of Organic Chemistry. 2014 ; Vol. 79, No. 1. pp. 7-24.
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Total syntheses of the monoterpene indole alkaloids (±)- alstilobanine A and e and (±)-angustilodine. / Feng, Yiqing; Majireck, Max M.; Weinreb, Steven M.

In: Journal of Organic Chemistry, Vol. 79, No. 1, 03.01.2014, p. 7-24.

Research output: Contribution to journalArticle

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