Steroids and related natural products. Part XCI. Synthesis of the cardenolides canarigenin and uzarigenin

Yoshiaki Kamano; George Pettit; Machiko Tozawa

doi:10.1039/P19750001972

Steroids and related natural products. Part XCI. Synthesis of the cardenolides canarigenin and uzarigenin

Yoshiaki Kamano, George Pettit, Machiko Tozawa

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1 Scopus citations

Abstract

From 3β,14-dihydroxy-5β,14β-card-20(22)-enolide (digitoxigenin)(III), new formal total syntheses of canarigenin [3β,14-dihydroxy-14β-carda-4,20(22)-dienolide](IIa) and uzarigenin [3β,14-dihydroxy-5α,14β-card-20(22)-enolide](Ic) have been completed. The route found most convenient involved direct oxidation of digitoxigenin (III) with t-butyl hypochlorite to yield the 4β-chloro-3-ketone (IVb). Dehydrohalogenation to the 4-en-3-one (canarigenone)(V) was followed by selective reduction with lithium hydrido-tri-t-butoxyaluminate to afford canarigenin (IIa) and with lithium borohydride to yield uzarigenin (Ic).

Original language	English (US)
Pages (from-to)	1972-1976
Number of pages	5
Journal	Journal of the Chemical Society, Perkin Transactions 1
Issue number	19
DOIs	https://doi.org/10.1039/P19750001972
State	Published - Jan 1 1975

ASJC Scopus subject areas

Chemistry(all)

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title = "Steroids and related natural products. Part XCI. Synthesis of the cardenolides canarigenin and uzarigenin",

abstract = "From 3β,14-dihydroxy-5β,14β-card-20(22)-enolide (digitoxigenin)(III), new formal total syntheses of canarigenin [3β,14-dihydroxy-14β-carda-4,20(22)-dienolide](IIa) and uzarigenin [3β,14-dihydroxy-5α,14β-card-20(22)-enolide](Ic) have been completed. The route found most convenient involved direct oxidation of digitoxigenin (III) with t-butyl hypochlorite to yield the 4β-chloro-3-ketone (IVb). Dehydrohalogenation to the 4-en-3-one (canarigenone)(V) was followed by selective reduction with lithium hydrido-tri-t-butoxyaluminate to afford canarigenin (IIa) and with lithium borohydride to yield uzarigenin (Ic).",

author = "Yoshiaki Kamano and George Pettit and Machiko Tozawa",

year = "1975",

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doi = "10.1039/P19750001972",

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journal = "Journal of the Chemical Society, Perkin Transactions 1",

issn = "1470-4358",

publisher = "Chemical Society",

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TY - JOUR

T1 - Steroids and related natural products. Part XCI. Synthesis of the cardenolides canarigenin and uzarigenin

AU - Kamano, Yoshiaki

AU - Pettit, George

AU - Tozawa, Machiko

PY - 1975/1/1

Y1 - 1975/1/1

N2 - From 3β,14-dihydroxy-5β,14β-card-20(22)-enolide (digitoxigenin)(III), new formal total syntheses of canarigenin [3β,14-dihydroxy-14β-carda-4,20(22)-dienolide](IIa) and uzarigenin [3β,14-dihydroxy-5α,14β-card-20(22)-enolide](Ic) have been completed. The route found most convenient involved direct oxidation of digitoxigenin (III) with t-butyl hypochlorite to yield the 4β-chloro-3-ketone (IVb). Dehydrohalogenation to the 4-en-3-one (canarigenone)(V) was followed by selective reduction with lithium hydrido-tri-t-butoxyaluminate to afford canarigenin (IIa) and with lithium borohydride to yield uzarigenin (Ic).

AB - From 3β,14-dihydroxy-5β,14β-card-20(22)-enolide (digitoxigenin)(III), new formal total syntheses of canarigenin [3β,14-dihydroxy-14β-carda-4,20(22)-dienolide](IIa) and uzarigenin [3β,14-dihydroxy-5α,14β-card-20(22)-enolide](Ic) have been completed. The route found most convenient involved direct oxidation of digitoxigenin (III) with t-butyl hypochlorite to yield the 4β-chloro-3-ketone (IVb). Dehydrohalogenation to the 4-en-3-one (canarigenone)(V) was followed by selective reduction with lithium hydrido-tri-t-butoxyaluminate to afford canarigenin (IIa) and with lithium borohydride to yield uzarigenin (Ic).

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