Carbon‐13 NMR spectra of bile acid derivatives. Part III. Unsaturated 5β‐cholanoic acids

Iida, Takashi; Goto, Junichi; Nambara, Toshio

doi:10.1002/mrc.1260310423

Cited by 6 publications

(5 citation statements)

References 12 publications

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“…The 13 C-NMR spectra revealed that compounds 9 and 10 had a tetrasubstituted double bond, whereas compound 6 was trisubstituted. The chemical shifts of 13 C signals in 6 and 10 were in good agreement with those reported in the literature (23). The remaining tetrasubstituted alkene 9, there- C-8 (130.1 ppm) and C-9 (131.7 ppm) in 9 were similar to those reported (128.3 and 134.9 ppm, respectively) for 3a-hydroxy-5a-cholest-8-ene (24).…”

Section: Synthesis Of 15a-hydroxylithocholic Acidsupporting

confidence: 89%

Isolation and chemical synthesis of a major, novel biliary bile acid in the common wombat (Vombatus ursinus): 15α-hydroxylithocholic acid

Kakiyama

Tamegai

Iida

et al. 2007

Journal of Lipid Research

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The major bile acids present in the gallbladder bile of the common Australian wombat (Vombatus ursinus) were isolated by preparative HPLC and identified by NMR as the taurine N-acylamidates of chenodeoxycholic acid (CDCA) and 15a-hydroxylithocholic acid (3a,15a-dihydroxy5b-cholan-24-oic acid). Taurine-conjugated CDCA constituted 78% of biliary bile acids, and (taurine-conjugated) 15a-hydroxylithocholic acid constituted 11%. Proof of structure of the latter compound was obtained by its synthesis from CDCA via a # 14 intermediate. The synthesis of its C-15 epimer, 15b-hydroxylithocholic acid (3a,15b-dihydroxy-5b-cholan-24-oic acid), is also reported. The taurine conjugate of 15a-hydroxylithocholic acid was synthesized and shown to have chromatographic and spectroscopic properties identical to those of the compound isolated from bile. It is likely that 15a-hydroxylithocholic acid is synthesized in the wombat hepatocyte by 15a-hydroxylation of lithocholic acid that was formed by bacterial 7a-dehydroxylation of CDCA in the distal intestine. Thus, the wombat appears to use 15a-hydroxylation as a novel detoxification mechanism for lithocholic acid

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Section: Synthesis Of 15a-hydroxylithocholic Acidsupporting

confidence: 89%

Isolation and chemical synthesis of a major, novel biliary bile acid in the common wombat (Vombatus ursinus): 15α-hydroxylithocholic acid

Kakiyama

Tamegai

Iida

et al. 2007

Journal of Lipid Research

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“…The results are compiled in Table 1. The 13 C resonances in the parent steroid nucleus were exclusively assigned by measuring the 13 C DEPT spectra and by comparing with those of analogous steroids reported previously (Iida et al, 1993). The methine and methylene protons bonded to each of the carbon atoms in 1-3 were assigned by correlating the cross peaks in the 1 H-13 C HETCOR spectra.…”

Section: Resultsmentioning

confidence: 99%

Nuclear magnetic resonance spectroscopy of 3β,7β-dihydroxy-5-cholen-24-oic acid multi-conjugates: unusual bile acid metabolites in human urine

Kakiyama

Ogawa

Iida

et al. 2006

Chemistry and Physics of Lipids

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“…Compound 5 was obtained by reduction of the a,b-unsaturated ester described above with diisobutylaluminum hydride, followed by aqueous acid treatment. Compound 10 44,45) was obtained by esterification of cholenic acid 16 (purchased from Steraloids Inc. Wilton, NH, U.S.A., Chart 2) with trimethylsilyldiazomethane. 46) Compound 4 47) was prepared by LiAlH 4 reduction of compound 10.…”

Section: Methodsmentioning

confidence: 99%

Coordination of Sodium Cation to an Oxygen Function and Olefinic Double Bond to Form Molecular Adduct Ion in Fast Atom Bombardment Mass Spectrometry.

Morisaki

Kobayashi

Yamamura

et al. 2002

CHEMICAL & PHARMACEUTICAL BULLETIN

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One of the most important uses of mass spectrometry in organic chemistry is in the determination of molecular weight (MW: M). In fast atom bombardment (FAB) mass spectrometry, 1-3) molecular-related ion peaks of organic compounds are generally observed as [MϩH] ϩ , [M] ϩ , [MϪH] ϩ or [Mϩ2H] ϩ (for positive ion), depending on the structures. However, compounds which decompose during the analyses show only very weak or no molecular-related ion peaks. In such cases, addition of an alkali metal salt to the compounds sometimes helps to induce adduct ion peaks [MϩA] ϩ (A: atomic weight of alkali metal), and these peaks have also been used for molecular weight determination in FAB mass spectrometry. 4-7)Alkali metal adduct ions of organic compounds are observed in FAB mass analyses of various compounds, especially polyoxygenated compounds such as saccharides [8][9][10][11] and polyethers, [12][13][14][15] and polyfunctional compounds such as peptides. [16][17][18][19] We previously reported the structural requirements of oxygen functional groups for stabilization of the adduct ions in FAB mass spectra of a variety of diols and related compounds with the addition of NaCl. 7) Compounds with two proximal oxygens efficiently coordinated to Na ϩ , and afforded the adduct ion peaks [MϩNa] ϩ [Chart 1a]. However, compounds with an isolated hydroxyl group or ether oxygen hardly formed a complex with Na ϩ , and the intensities of the Na ϩ adduct ion peaks were negligible compared to those of diols, including n-hexadecane-1,2-diol (12), which formed stable Na ϩ adduct ions.7)The affinity of alkali metal cations to p-electrons has been extensively investigated on the basis of cation p-interactions. [20][21][22][23][24][25][26][27][28] Experiments to determine the binding energies of alkali metal cations with benzene and ethylene in the gas phase have been carried out by mass analyses of ion-molecule binding under solvent-free conditions and without counter ion influence. [22][23][24] Theoretical studies have also been carried out to calculate the binding energies of alkali metal cations to aromatic compounds.25-27) As described above, our previous studies showed that compounds with an isolated hydroxyl group hardly formed a complex with Na ϩ under FAB mass spectrometric conditions. 7) However, if an olefinic double bond and Na ϩ could interact, allylic alcohols might form a complex with Na ϩ by the participation of both the hydroxyl group and the olefinic double bond to yield [MϩNa] ϩ ion peaks effectively [Chart 1b]. Allylic alcohols are susceptible to dehydroxylation (protonation followed by dehydration to form the allylic cation) under FAB mass spectrometric conditions, but if the hydroxyl group and olefinic double bond were coordinated to Na ϩ , the complex might not readily undergo dehydroxylation, as in the case of 1,2-diols. 7)This paper reports the interactions of Na ϩ with allylic alcohols in FAB mass spectrometry. Steroidal allylic alcohols, in which a,b-unsaturated hydroxyl groups were located in ring A ...

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Carbon‐13 NMR spectra of bile acid derivatives. Part III. Unsaturated 5β‐cholanoic acids

Abstract: 33,378 (1978). 2. A. Lévai and J. 0 . Schág, Pharrnazie 34,749 (1 979).

Cited by 6 publications

References 12 publications

Isolation and chemical synthesis of a major, novel biliary bile acid in the common wombat (Vombatus ursinus): 15α-hydroxylithocholic acid

Isolation and chemical synthesis of a major, novel biliary bile acid in the common wombat (Vombatus ursinus): 15α-hydroxylithocholic acid

Nuclear magnetic resonance spectroscopy of 3β,7β-dihydroxy-5-cholen-24-oic acid multi-conjugates: unusual bile acid metabolites in human urine

Coordination of Sodium Cation to an Oxygen Function and Olefinic Double Bond to Form Molecular Adduct Ion in Fast Atom Bombardment Mass Spectrometry.

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