Hydroxy-steroids. Part XI. The preparation and infrared spectra of vicinal cholestanediols

Davey, C. W.; McGinnis, E. L.; McKeown, J. M.; Meakins, G. D.; Pemberton, M. W.; Young, R. N.

doi:10.1039/j39680002674

Cited by 20 publications

(14 citation statements)

References 2 publications

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“…As previously reported for comparable examples, 51 the treatment with catalytic amounts of OsO 4 and NMO as stoichiometric oxidant favors in our case the formation of the unde- sired 2α,3α-cis-diol 22, whereas the corresponding 2β,3β-cisdiols are reported to be prepared by the addition of iodine followed by a nucleophilic displacement with acetate in the presence of water and the hydrolysis of the intermediately formed ester using AgOAc, 52,53 Tl(OAc) 3 54 or CuOAc. 55 Driven by the idea of a direct conversion of androst-2-ene to the corresponding 2,3-cis-diol, we contemplated a Sharpless dihydroxylation adjusting the side of attack by the choice of the ligand.…”

Section: Resultssupporting

confidence: 81%

Towards the synthesis of calotropin and related cardenolides from 3-epiandrosterone: A-ring related modifications

2020

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Section: Resultssupporting

confidence: 81%

Towards the synthesis of calotropin and related cardenolides from 3-epiandrosterone: A-ring related modifications

2020

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“…CD has been of considerable interest by itself and has been studied previously by X-ray diffraction, 17 matrix isolation spectroscopy 18 and in more or less inert solvents. [18][19][20][21][22][23] As our work confirms as a side effect (see ESI †), there are substantial spectral shifts induced by such environments. 24 Furthermore, the energy sequence between cyclic and open intermolecular hydrogen bond patterns is likely to change by adding a solvent or matrix enclosure which can act as a hydrogen bond acceptor.…”

Section: Introductionmentioning

confidence: 61%

The reduced cohesion of homoconfigurational 1,2-diols

Hartwig

Lange

Poblotzki

et al. 2020

Phys. Chem. Chem. Phys.

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By a combination of linear FTIR and Raman jet spectroscopy, racemic trans-1,2-cyclohexanediol is shown to form an energetically unrivalled S 4 -symmetric heterochiral dimer in close analogy to 1,2-ethanediol.Analogous experiments with enantiopure trans-1,2-cyclohexanediol reveal the spectral signature of at least three unsymmetric homochiral dimers. A comparison to signal-enhanced spectra of 1,2-ethanediol and to calculations uncovers at least three transiently homochiral dimer contributions as well. In few of these dimer structures, the intramolecular OHÁ Á ÁO contact present in monomeric 1,2-diols survives, despite the kinetic control in supersonic jet expansions. This provides further insights into the dimerisation mechanism of conformationally semi-flexible molecules in supersonic jets. Racemisation upon dimerisation is shown to be largely quenched under jet cooling conditions, whereas it should be strongly energy-driven at higher temperatures. The pronounced energetic preference for heterochiral aggregation of vicinal diols is also discussed in the context of chirality-induced spin selectivity. † Electronic supplementary information (ESI) available: Interactive and static structures, tables of experimental and computational details, energy diagrams for different levels of calculation, and additional experimental spectra. See

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“…et i.r. avec le produit de reference obtenu par I'ouverture des Bpoxydes correspondants (12). Les points de fusions sont identiques, p.f.…”

Section: ( 3 ) Oxydation Du Tert-butyl-4 Cyclohex8neunclassified

Oxydation des alcènes par l'ion thallique. I. Stéréochimie et mécanisme de l'oxydation des cyclohexènes

Freppel¹,

Favier²,

Richer³

et al. 1971

Can. J. Chem.

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R e~u le 15 mars 1971 L'Ctude de la stBrBochimie des diols form& dans I'oxydation du tert-butyl-3 cyclohexene par le sulfate thallique a permis de mettre en Bvidence la participation du groupe hydroxyle en a lors de la rupture de la liaison C-TI de I'intermBdiaire organothalleux. En effet, seuls les diols trans ont Bt B obtenus ce qui exclut la substitution SN2 par I'eau. I1 est suggQB que l'oxydation thallique en milieu aqueux peut constituer une synthese en une seule Btape de diols trans dans le cas des systkmes rigides oh l'organothalleux intermdiaire a une configuration diaxiale. La formation d'un seul diol diaxial lors de l'oxydation du tert-butyl-4 cyclohexene tend ti confirmer cette hypothbe.The stereochemistry of the diols obtained by oxidation of 3-t-butylcyclohexene by thallic sulfate indicates that the a hydroxyl group participates in the breaking of the C-T1 bond of the intermediate organothallous compound. The fact that only the trans diols are obtained indicates that an SN2 substitution of the thallium can be excluded. We suggest that the thallic oxidation in aqueous media of olefin of rigid conformation is an excellent one-step method of preparing trans diols. The formation of the trans diaxial diol upon oxidation of 4-t-butylcyclohexene tends to confirm that hypothesis.

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Hydroxy-steroids. Part XI. The preparation and infrared spectra of vicinal cholestanediols

Cited by 20 publications

References 2 publications

Towards the synthesis of calotropin and related cardenolides from 3-epiandrosterone: A-ring related modifications

Towards the synthesis of calotropin and related cardenolides from 3-epiandrosterone: A-ring related modifications

The reduced cohesion of homoconfigurational 1,2-diols

Oxydation des alcènes par l'ion thallique. I. Stéréochimie et mécanisme de l'oxydation des cyclohexènes

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