STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. II. SYNTHESIS OF β-SUBSTITUTED Δα,β-BUTENOLIDES FROM ι-ACETOXYMETHYL KETONES

LINVILLE, ROBERT G.; ELDERFIELD, ROBERT C.

doi:10.1021/jo01202a011

Cited by 15 publications

(6 citation statements)

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“…In the case of IX, where R is phenyl, treatment of the free acid (X) with a solution of hydrogen bromide in glacial acetic acid gave /3-phenyl^" ^-butenolide (XII). Evidence for the structure assigned to XII was obtained by its synthesis by ring closure of the substance prepared by oxidation of ethyl ß-methylcinnamate with selenium dioxide (13) and also by ring closure and dehydration of ethyl /3-phenyl-/3-hydroxy-Y-acetoxybutyrate (17). The formation of XII can then be pictured as resulting from the series of reactions IX-XII.…”

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confidence: 99%

STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. I. SYNTHESIS OF β-SUBSTITUTED Δ^α,β-BUTENOLIDES FROM ι-METHOXYMETHYL KETONES

Rubin¹,

Paist²,

Elderfield³

1941

J. Org. Chem.

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The group of naturally occurring substances known as the cardiac drugs forms an interesting division of the large group of steroids. These substances have been grouped together on the basis of a common pharmacodynamic action on the heart. The investigations, chiefly of Jacobs, Windaus, Tschesche, and Stoll, have provided ample evidence, which has been adequately reviewed in numerous publications (1), for assigning structures to the more important members of the group. With the exception of the toad venoms and a few other substances of alkaloidal nature, the drugs are all non-nitrogenous glycosides which on hydrolysis with acid break with greater or less ease into the aglycones and constituent sugars. The major portion of the physiological action of the glycosides has been found to reside in the aglycone portion of the molecule, although the nature of the sugar moiety plays a definite but relatively minor part in determining the quantitative action of the drugs (2). For purposes of chemical classification it is convenient to subdivide the group of aglycones on the basis of the structure of the side chain. Thus one finds a large group of aglycones, which can be called the "digitalis-strophanthus group," characterized by a side chain consisting of the lactone of an enolized |8-aldehydo acid carrying the cyclopentanophenanthrene ring system as a substituent on the /3-carbon atom (type formula I), and a second and smaller group, which may be designated the "squill-toad venom group," in which the side chain is an -pyrone substituted in the 5-position (type formula II).

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STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. I. SYNTHESIS OF β-SUBSTITUTED Δ^α,β-BUTENOLIDES FROM ι-METHOXYMETHYL KETONES

Rubin¹,

Paist²,

Elderfield³

1941

J. Org. Chem.

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“…Treatment of 20 with Zn and ethyl bromoacetate followed by hydrolysis and cyclization with AcOH and 38% aq HCl gave the α,β-unsaturated γ-butyrolactone 22 in 70% yield [11b,14]. Catalytic hydrogenation of 22 with H 2 -Pd/C in EtO-Ac afforded 3 in 96% yield [14]. Similarly, treatment of 21 gave 23 in 40% yield, whose reduction with NaBH 4 in MeOH afforded 4 in 95% yield [11b,14].…”

Section: Resultsmentioning

confidence: 99%

Preparation of (+)- and (−)- β-phenyl- and β-(4-chlorophenyl)-γ- butyrolactones: Key Intermediates in the Synthesis of β-phenyl-GABA and Baclofen

Meléndez-Rodrı́guez¹

2017

J. Mex. Chem. Soc.

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The preparation of b-phenyl- and b-(4-chlorophenyl)-g-butyrolactones (±)-3 and (±)-4 and their resolution to the corresponding (+)-(S)-3, (-)-(R)-3 and (+)-(S)-4, (-)-(R)-4 through formation, flash column chromatography separation and subsequent hydrolysis of diastereoisomeric 4-hydroxybutyramides (2’R,3S)-5, (2’R,3R)-5, (2’R,3S)-6 and (2’R,3R)-6 is described. The absolute configuration assignment of enantiopure 3 and 4 was supported by X-ray crystallographic structures of (2’R,3R)-5, (2’R,3S)-6 and (2’R,3R)-6.

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“…Inasmuch as the halides required as starting material for this synthesis are not readily available in the steroid series, the use of acetoxymethyl or benzoxymethyl alkyl ketones rather than the methoxymethyl ketones was investigated (75,76,144). These substances are easily obtained from the appropriate etio acids through the acid chlorides and diazoketones (162), or in certain cases from the corresponding methyl ketones with lead tetraacetate (14,123).…”

Section: B Synthetic Glycosides From Natural Geninsmentioning

confidence: 99%

“…By application of the methods described above ,/3-butenolides substituted in the /3-position by the following groups have been prepared: cyclohexyl (75), 4-hydroxycyclohexyl (28, 29), 3,4-dihydroxycyclohexyl (27), phenyl (75,173), p-hydroxyphenyl (82), -hydroxyphenyl (82), decahydro-/3-naphthyl (68), 6-hydroxy-2-naphthyl (68), 1-hydrindanyl (68), etiocholanyl (76), 3(a)hydroxyetiocholanyl (130), 3(/3)-hydroxyetiocholanyl (76), 3(a), 12(a)-dihydroxyetiocholanyl (142), 3(a),7(a), 12(a)-trihydroxyetiocholanyl (34), etioallocholanyl (106), A2-etioallocholenyl (97), 3(a)-hydroxyetioallocholanyl (106), 3(/3)-hydroxyetioallocholanyl (106,132,137) (137, 143), 2,3-dihydroxyetioallocholanyl (97), 3(/3),5-dihydroxyetioallocholanyl (138), 3(/3)-hydroxy-A5-etiocholenyl (99, 131, 144), 3(/3)-hydroxyetioallocholanylmethyl (98), 3(S)-hydroxy-A5-etioallocholenylmethyl (98), norcholanyl (67), 3(/3)-hydroxv-A5-norcholenyl (99,134), and 3(a),7(a), 12(a)-trihydroxynorcholanyl (67,135). Allouzarigenin has also been prepared (109).…”

Section: B Synthetic Glycosides From Natural Geninsmentioning

confidence: 99%

Structure and Synthesis of Cardiac Genins.

Turner¹

1948

Chem. Rev.

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STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. II. SYNTHESIS OF β-SUBSTITUTED Δ^α,β-BUTENOLIDES FROM ι-ACETOXYMETHYL KETONES

Cited by 15 publications

References 3 publications

STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. I. SYNTHESIS OF β-SUBSTITUTED Δ^α,β-BUTENOLIDES FROM ι-METHOXYMETHYL KETONES

STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. I. SYNTHESIS OF β-SUBSTITUTED Δ^α,β-BUTENOLIDES FROM ι-METHOXYMETHYL KETONES

Preparation of (+)- and (−)- β-phenyl- and β-(4-chlorophenyl)-γ- butyrolactones: Key Intermediates in the Synthesis of β-phenyl-GABA and Baclofen

Structure and Synthesis of Cardiac Genins.

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STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. II. SYNTHESIS OF β-SUBSTITUTED Δα,β-BUTENOLIDES FROM ι-ACETOXYMETHYL KETONES

Cited by 15 publications

References 3 publications

STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. I. SYNTHESIS OF β-SUBSTITUTED Δα,β-BUTENOLIDES FROM ι-METHOXYMETHYL KETONES

STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. I. SYNTHESIS OF β-SUBSTITUTED Δα,β-BUTENOLIDES FROM ι-METHOXYMETHYL KETONES

Preparation of (+)- and (−)- β-phenyl- and β-(4-chlorophenyl)-γ- butyrolactones: Key Intermediates in the Synthesis of β-phenyl-GABA and Baclofen

Structure and Synthesis of Cardiac Genins.

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STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. II. SYNTHESIS OF β-SUBSTITUTED Δ^α,β-BUTENOLIDES FROM ι-ACETOXYMETHYL KETONES

STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. I. SYNTHESIS OF β-SUBSTITUTED Δ^α,β-BUTENOLIDES FROM ι-METHOXYMETHYL KETONES

STUDIES ON LACTONES RELATED TO THE CARDIAC AGLYCONES. I. SYNTHESIS OF β-SUBSTITUTED Δ^α,β-BUTENOLIDES FROM ι-METHOXYMETHYL KETONES