Bufadienolides. 5. Synthesis of cardenolides

George Pettit, Cherry L. Herald, John P. Yardley

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

Boron trifluoride catalyzed lead tetraacetate oxidation of 3β-acetoxy-20-oxo-5α-pregnane and of pregnenolone acetate was employed to obtain the corresponding 21-acetoxy derivatives. Reaction of 3β,21-diacetoxy-20-oxo-5α-pregnane (1) with the anion prepared from diethyl cyanomethylphosphonate and subsequent treatment with hydrochloric acid afforded the corresponding nitrile (2) and derived imino lactone hydrochloride (3a). Acid hydrolysis of the imino lactone gave 3β-acetoxy-5α-cardenolide (4b). Analogous transformation of ketone 6 provided 3β-acetoxy-Δ5-cardenolide (10b). The two-step reaction sequence from readily available α-hydroxy ketones provides a potentially useful route to imino lactones and butenolides.

Original languageEnglish (US)
Pages (from-to)1389-1392
Number of pages4
JournalJournal of Organic Chemistry
Volume35
Issue number5
StatePublished - 1970

Fingerprint

Bufanolides
Cardenolides
Lactones
Pregnanes
Ketones
Pregnenolone
Nitriles
Hydrochloric Acid
Anions
Hydrolysis
Acetates
Derivatives
Oxidation
Acids

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Pettit, G., Herald, C. L., & Yardley, J. P. (1970). Bufadienolides. 5. Synthesis of cardenolides. Journal of Organic Chemistry, 35(5), 1389-1392.

Bufadienolides. 5. Synthesis of cardenolides. / Pettit, George; Herald, Cherry L.; Yardley, John P.

In: Journal of Organic Chemistry, Vol. 35, No. 5, 1970, p. 1389-1392.

Research output: Contribution to journalArticle

Pettit, G, Herald, CL & Yardley, JP 1970, 'Bufadienolides. 5. Synthesis of cardenolides', Journal of Organic Chemistry, vol. 35, no. 5, pp. 1389-1392.
Pettit, George ; Herald, Cherry L. ; Yardley, John P. / Bufadienolides. 5. Synthesis of cardenolides. In: Journal of Organic Chemistry. 1970 ; Vol. 35, No. 5. pp. 1389-1392.
@article{8fd142345d6b498db0b0ad68a24558cb,
title = "Bufadienolides. 5. Synthesis of cardenolides",
abstract = "Boron trifluoride catalyzed lead tetraacetate oxidation of 3β-acetoxy-20-oxo-5α-pregnane and of pregnenolone acetate was employed to obtain the corresponding 21-acetoxy derivatives. Reaction of 3β,21-diacetoxy-20-oxo-5α-pregnane (1) with the anion prepared from diethyl cyanomethylphosphonate and subsequent treatment with hydrochloric acid afforded the corresponding nitrile (2) and derived imino lactone hydrochloride (3a). Acid hydrolysis of the imino lactone gave 3β-acetoxy-5α-cardenolide (4b). Analogous transformation of ketone 6 provided 3β-acetoxy-Δ5-cardenolide (10b). The two-step reaction sequence from readily available α-hydroxy ketones provides a potentially useful route to imino lactones and butenolides.",
author = "George Pettit and Herald, {Cherry L.} and Yardley, {John P.}",
year = "1970",
language = "English (US)",
volume = "35",
pages = "1389--1392",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "5",

}

TY - JOUR

T1 - Bufadienolides. 5. Synthesis of cardenolides

AU - Pettit, George

AU - Herald, Cherry L.

AU - Yardley, John P.

PY - 1970

Y1 - 1970

N2 - Boron trifluoride catalyzed lead tetraacetate oxidation of 3β-acetoxy-20-oxo-5α-pregnane and of pregnenolone acetate was employed to obtain the corresponding 21-acetoxy derivatives. Reaction of 3β,21-diacetoxy-20-oxo-5α-pregnane (1) with the anion prepared from diethyl cyanomethylphosphonate and subsequent treatment with hydrochloric acid afforded the corresponding nitrile (2) and derived imino lactone hydrochloride (3a). Acid hydrolysis of the imino lactone gave 3β-acetoxy-5α-cardenolide (4b). Analogous transformation of ketone 6 provided 3β-acetoxy-Δ5-cardenolide (10b). The two-step reaction sequence from readily available α-hydroxy ketones provides a potentially useful route to imino lactones and butenolides.

AB - Boron trifluoride catalyzed lead tetraacetate oxidation of 3β-acetoxy-20-oxo-5α-pregnane and of pregnenolone acetate was employed to obtain the corresponding 21-acetoxy derivatives. Reaction of 3β,21-diacetoxy-20-oxo-5α-pregnane (1) with the anion prepared from diethyl cyanomethylphosphonate and subsequent treatment with hydrochloric acid afforded the corresponding nitrile (2) and derived imino lactone hydrochloride (3a). Acid hydrolysis of the imino lactone gave 3β-acetoxy-5α-cardenolide (4b). Analogous transformation of ketone 6 provided 3β-acetoxy-Δ5-cardenolide (10b). The two-step reaction sequence from readily available α-hydroxy ketones provides a potentially useful route to imino lactones and butenolides.

UR - http://www.scopus.com/inward/record.url?scp=0014781354&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0014781354&partnerID=8YFLogxK

M3 - Article

VL - 35

SP - 1389

EP - 1392

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 5

ER -