STEROIDS. XIV.<sup>1</sup> STUDIES IN THE 3,6-DIHYDROXYPREGNANE SERIES (PART I)

Mancera, O.; Rosenkranz, G.; Djerassi, Carl

doi:10.1021/jo01142a005

Cited by 16 publications

(8 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…• Analogous hydrogenation of ß, 6/3-diacetoxy-A4-unsaturated steroids leads to the alloconfiguration (6). Ethyl 8ß,19-dibenzoxy-S-hydroxyetiocholanate (Ha).…”

Section: Methodsmentioning

confidence: 99%

“…Treatment with diazoethane of the mixture of VIII and Villa represented a third route for the preparation of VII. 6. Acetylation of XII gave methyl 38,19-diacetoxy-A4-etiocholenate (XIII) which by catalytic hydrogenation (Pt, acetic acid) gave a mixture of methyl 19-acetoxyetio(alio?…”

Section: Methodsmentioning

confidence: 99%

“…cf. 8) 6. Analogous cases regarding the order of chromatographic elution from aluminum oxide are: cholestane-3a-ol followed by cholestane-3/3-ol (9) and coprostane-Sa-ol closely followed by coprostane-3/S-ol(10).…”

mentioning

confidence: 99%

See 2 more Smart Citations

INVESTIGATIONS ON STEROIDS. XVII. DEHYDRATION STUDIES IN THE SERIES OF 3β, 5, 19-TRIHYDROXYETIOCHOLANIC ACID^*1

Herzig¹,

Ehrenstein²

1952

J. Org. Chem.

View full text Add to dashboard Cite

As has been stated previously (2,3) it is intended to synthesize certain analogs of steroid hormones where the angular carbon atom between rings A and B is either missing (19-nor compounds) or is present in an oxygenated form, i.e. as a primary alcohol, aldehyde, or carboxyl group. In particular, compounds structurally derived from progesterone, 11-desoxycorticosterone, and 17-hydroxy-lldesoxycorticosterone (Reichstein's substance S) are of interest. A promising starting material appeared to be ethyl 3/3,5,19-trihydroxyetiocholanate (I) which in turn can be obtained by partial synthesis from strophanthidin (1, 2). The purpose of the present investigation was the conversion of I into further suitable intermediates towards this general aim.In an earlier publication (3) it was shown that, by means of N-bromoacetamide, I can be selectively oxidized to ethyl 3-keto-5,19-dihydroxyetiocholanate which under the influence of Girard's Reagent T is smoothly dehydrated to ethyl 3keto-19-hydroxy-A4-etiocholenate (IX). It has been found that the free 3/3,5,19trihydroxyetiocholanic acid (III), as obtained by saponification of I, can be subjected to the same reaction. Thus, when III was oxidized with N-bromoacetamide, followed by suitable treatment of the reaction product with Girard's Reagent T, a satisfactory yield of 3-keto-19-hydroxy-A4-etiocholenic acid (X) was obtained. The methyl ester (XI) and the known ethyl ester (IX) (3) were

show abstract

“…• Analogous hydrogenation of ß, 6/3-diacetoxy-A4-unsaturated steroids leads to the alloconfiguration (6). Ethyl 8ß,19-dibenzoxy-S-hydroxyetiocholanate (Ha).…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

INVESTIGATIONS ON STEROIDS. XVII. DEHYDRATION STUDIES IN THE SERIES OF 3β, 5, 19-TRIHYDROXYETIOCHOLANIC ACID^*1

Herzig¹,

Ehrenstein²

1952

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…± The dihydroxylation of ( ± )-isopulegol was performed with formic acid (HCOOH) and 30% aqueous hydrogen peroxide (H 2 O 2 ), followed by alkaline hydrolysis [14] [15]. H 2 O 2 was slowly added to a solution of ( ± )-isopulegol and HCOOH at 508, and the reaction was monitored by gas chromatography (GC).…”

Section: Of ( ± )-Isopulegol ( (1r2s5r)-5-methyl-2-(1-methylethenylmentioning

confidence: 99%

Synthesis and Absolute Configuration at C(8) of ‘p‐Menthane‐3,8,9‐triol’ Derived from (–)‐Isopulegol

Yuasa

2004

Helvetica Chimica Acta

View full text Add to dashboard Cite

Two diastereoisomers of the new, potentially insecticidal ‘p‐menthane‐3,8,9‐triol’ (=(2S)‐ and (2R)‐ 2‐[(1R,2R,4R)‐2‐hydroxy‐4‐methylcyclohexyl]propane‐1,2‐diol; (8S)‐ and (8R)‐1), have been synthesized from (–)‐isopulegol by both conventional dihydroxylation and catalytic Sharpless dihydroxylation (Scheme). The absolute configuration at C(8) of the corresponding orthoformate adduct (8S)‐3a was determined by 1H‐NMR and X‐ray crystallographic analysis (Figure).

show abstract

“…134-136", identified by a mixture melting point determination and infrared comparison with an authentic sample (10). of collidine, the collidine hydrobromide was filtered, and the product was extracted with ether, washed until neutral, dried, and evaporated.…”

Section: A5-pregnene-3@ 10@-diol-7-one Diacetate (I)mentioning

confidence: 99%

Steroids. XXXVI. Desulfurization Experiments in the 7-Ketopregnane Series

Romo¹,

Rosenkranz²,

Djerassi³

1952

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

7,ll-Diketones of the steroid series represent important intermediates in several syntheses of 11-oxygenated steroids from ring-C unsubstituted precursors and the removal of the 7-keto group is usually the penultimate step. I n a number of instances (1-3) this is accomplished by formation of the cycloethylene mercaptol followed by Raney nickel desulfurization according to the procedure first introduced into the steroid series by Rauptmann (4). At the present time, the C-11 oxygen introduction methods have been applied only to ring-C unsubstituted steroids with the alZo configuration a t C-5 (a). Since the corresponding saturated "normal" (5 P ) and A*-unsaturated 11-oxygenated derivatives are of very considerable importance and might possibly be obtainable from the intermediate 7,ll-diketones of the d o series, there were carried out certain model experiments with A5-pregnene-3p , 20p-diol-7-one diacetate (I) in order to study

show abstract

STEROIDS. XIV.¹ STUDIES IN THE 3,6-DIHYDROXYPREGNANE SERIES (PART I)

Cited by 16 publications

References 7 publications

INVESTIGATIONS ON STEROIDS. XVII. DEHYDRATION STUDIES IN THE SERIES OF 3β, 5, 19-TRIHYDROXYETIOCHOLANIC ACID^*1

INVESTIGATIONS ON STEROIDS. XVII. DEHYDRATION STUDIES IN THE SERIES OF 3β, 5, 19-TRIHYDROXYETIOCHOLANIC ACID^*1

Synthesis and Absolute Configuration at C(8) of ‘p‐Menthane‐3,8,9‐triol’ Derived from (–)‐Isopulegol

Steroids. XXXVI. Desulfurization Experiments in the 7-Ketopregnane Series

Contact Info

Product

Resources

About

STEROIDS. XIV.1 STUDIES IN THE 3,6-DIHYDROXYPREGNANE SERIES (PART I)

Cited by 16 publications

References 7 publications

INVESTIGATIONS ON STEROIDS. XVII. DEHYDRATION STUDIES IN THE SERIES OF 3β, 5, 19-TRIHYDROXYETIOCHOLANIC ACID*1

INVESTIGATIONS ON STEROIDS. XVII. DEHYDRATION STUDIES IN THE SERIES OF 3β, 5, 19-TRIHYDROXYETIOCHOLANIC ACID*1

Synthesis and Absolute Configuration at C(8) of ‘p‐Menthane‐3,8,9‐triol’ Derived from (–)‐Isopulegol

Steroids. XXXVI. Desulfurization Experiments in the 7-Ketopregnane Series

Contact Info

Product

Resources

About

STEROIDS. XIV.¹ STUDIES IN THE 3,6-DIHYDROXYPREGNANE SERIES (PART I)

INVESTIGATIONS ON STEROIDS. XVII. DEHYDRATION STUDIES IN THE SERIES OF 3β, 5, 19-TRIHYDROXYETIOCHOLANIC ACID^*1

INVESTIGATIONS ON STEROIDS. XVII. DEHYDRATION STUDIES IN THE SERIES OF 3β, 5, 19-TRIHYDROXYETIOCHOLANIC ACID^*1