Retropinacol Rearrangement of 1α-Hydroxy Steroids. A New Route to 1β-Methyl 19-Norsteroids

Smith, Leland L.; Foell, Theodore; Teller, Daniel M.

doi:10.1021/jo01022a044

Cited by 10 publications

(2 citation statements)

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“…It is likely that there are marked differences of reactivity of the 5a-and 5f-epimers because of the proximity of alternating groups. It will also be necessary to consider the effects of elimination or rearrangement of the 19-methyl group in strong base, as discussed for la-hydroxy steroids by Smith, Foell & Teller (1965).…”

Section: Discussionmentioning

confidence: 99%

The partial characterization of 1-oxygenated steroids from urine of a hypertensive newborn child

Edwards

Trafford

1968

Biochemical Journal

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1. Four substances from the urine of a hypertensive newborn girl were partially characterized and shown to be 17oc-hydroxy-5, B-pregnane-1,3,20-trione, 3oc,17a-dihydroxy-5,B-pregnane-1,20-dione, 3a,17oc,20ac-trihydroxy-5p-pregnan-1-one and 5/3-pregnane-lB,3oc,17a,20c-tetrol. 2. The characterization rested mainly on RM analysis of the substances and their derivatives by glycol fission, providing evidence for position and degree of substitution and for steroidal character. Supporting evidence was provided by chemically specific location reactions. 3. Certain problems in the manipulation of these ,B-disubstituted steroids are discussed.The high 17-hydroxy corticosteroid excretion of patient S.C. when 1-3 weeks old and grossly hypertensive has been described elsewhere (Edwards, Harvey & Knight-Jones, 1968 MATERIALS AND METHODSFull details of the procedures used for the isolation of urinary steroids are described elsewhere (Edwards, 1968a) and in the present instance consisted of the following steps. Urine samples (6 days' collection, age between 8 and 20 days) from S.C. during her period of high 11-oxygenation index (ratio of metabolites of 17-hydroxylated precursors of cortisol to metabolites of cortisol; Edwards, Makin & Barratt, 1964) (Stevens, 1964). Each substance was homogeneous on the criterion that portions from the forward and rear portions ofa chromatographed zone on rechromatography gave zones side by side of identical RF values.The chemical transformations used were (i) borohydride reduction and (ii) periodate oxidation, both carried out as described by Edwards et al. (1964), and (iii) oxidation with Jones reagent carried out as described by Djerassi, Engle & Bowers (1956), but with trebled proportion of acetone. RM analysis procedure. RM values were calculated from RF values and referred to the root system of the family (light petroleum-methanol-water, 5:4:1, by vol.) as RMO values by correcting for the effects of benzene replacing light petroleum (Kabasakalian & Basch, 1960;Edwards, 1968a). Observed ARM values were compared with reference values (Table 1) and the latter used to indicate likely structural changes. For clarity the ARM value observed in changing from substance of structure A to structure B was signified ARM [A--B]. It was presumed that substances with RMO values differing by less than 0-07 (S.D. ofrepetition of a value on different occasions) were in fact one substance.Referencel-hydroxysteroid. loc-Hydroxy-5oc-androstane-3,17-dione samples from Dr Fukushima and Dr Foell were found to be identical with the exception of a small proportion of contaminant in the latter. This was assumed to be the lfl-isomer, since other isomerization was unlikely from the method of preparation. A similar contaminant was present in the lac-hydroxyandrost-4-ene-3,17-dione sample. The lc,3,B-dihydroxy-50c-androstan-17-one sample was uncontaminated.Other reference steroids were prepared by unambiguous chemical transformations and were purified by chromatography, but there was insufficient material available...

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Section: Discussionmentioning

confidence: 99%

The partial characterization of 1-oxygenated steroids from urine of a hypertensive newborn child

Edwards

Trafford

1968

Biochemical Journal

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“…In the epimeric series with the leaving group axial and anti-parallel to the angular methyl group, rearrangement of the methyl group takes place (358,361,362). Since the rates of acetolysis of (289) and its C4 axial epimer are only slightly affected by the p-methoxy substituent (k H I kocH, = 0.75 and 2.2, respectively), the transition state apparently bears little resemblance to the benzylic carbonium ions formed in the rearrangement (361).…”

Section: ~ Coh (283)mentioning

confidence: 99%

Biogenetic-Type Rearrangements of Terpenes

Coates

1976

Fortschritte Der Chemie Organischer Naturstoffe / Progress in the Chemistry of Organic Natural Products

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Modern Methods to Prepare Monofluoroaliphatic Compounds

Sharts

Sheppard

2011

Organic Reactions

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Organic fluorine chemistry has been important since the 1930s. The development of fluorine chemistry during World War II is well documented. Fluorine chemistry emerged in the 1950s because of three events: Large‐scale research designed to synthesize fluorine‐containing rockets was initiated. A fluorine atom at a specific site in a steroid molecule was found to enhance beneficial pharmacological effects New analytical techniques evolved (e.g., GC and NMR). There are eight reactions important for preparation of monofluoroaliphatic compounds. Halogen addition to alkenes and alkynes Fluoroalkylamine reagent for replacement of a hydoxy group. Nitrosyl fluoride addition to an activated double bond Hypofluorites for electrophilic fluorination. Inorganic and heteroatom fluorides for replacement of halogen, hydroxyl, or ester groups Hydrogen fluoride for addition Perchloryl fluoride for hydrogen replacement Condensation of a monolfluorinated organic compound.

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Retropinacol Rearrangement of 1α-Hydroxy Steroids. A New Route to 1β-Methyl 19-Norsteroids

Cited by 10 publications

References 1 publication

The partial characterization of 1-oxygenated steroids from urine of a hypertensive newborn child

The partial characterization of 1-oxygenated steroids from urine of a hypertensive newborn child

Biogenetic-Type Rearrangements of Terpenes

Modern Methods to Prepare Monofluoroaliphatic Compounds

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