51752-29-5Relevant articles and documents
Activity of antifungal organobismuth(III) compounds derived from alkyl aryl Ketones against S. cerevisiae: Comparison with a heterocyclic bismuth scaffold consisting of a diphenyl sulfone
Murafuji, Toshihiro,Tomura, Mai,Ishiguro, Katsuya,Miyakawa, Isamu
, p. 11077 - 11095 (2014/10/15)
A series of hypervalent organobismuth(III) compounds derived from alkyl aryl ketones [XBi(5-R′C6H3-2-COR)(Ar)] was synthesized to investigate the effect of the compounds' structural features on their antifungal activity against the yeast Saccharomyces cerevisiae. In contrast to bismuth heterocycles [XBi(5-RC6H3-2-SO 2C6H4-1′-)] derived from diphenyl sulfones, a systematic quantitative structure-activity relationship study was possible. The activity depended on the Ar group and increased for heavier X atoms, whereas lengthening the alkyl chain (R) or introducing a substituent (R′) reduced the activity. IBi(C6H4-2-COCH 3)(4-FC6H4) was the most active. Its activity was superior to that of the related acyclic analogues ClBi[C6H 4-2-CH2N(CH3)2](Ar) and ClBi(C 6H4-2-SO2 tert-Bu)(Ar) and also comparable to that of heterocyclic ClBi(C6H4-2-SO2C 6H4-1′-), which was the most active compound in our previous studies. Density function theory calculations suggested that hypervalent bismuthanes undergo nucleophilic addition with a biomolecule at the bismuth atom to give an intermediate ate complex. For higher antifungal activity, adjusting the lipophilicity-hydrophilicity balance, modeling the three-dimensional molecular structure around the bismuth atom, and stabilizing the ate complex appear to be more important than tuning the Lewis acidity at the bismuth atom.
Synthesis and First X-Ray Structure Analysis of a Stabilized Chiral Chlorobismuthine: Fixation of Molecular Geometry Induced by the Intramolecular Coordination of a Sulfonyl Group
Suzuki, Hitomi,Murafuji, Toshihiro,Azuma, Nagao
, p. 1169 - 1176 (2007/10/02)
A sulfonyl-stabilized chiral chlorobismuthine 1a was synthesized by the selective fluorodearylation of compound 3a with boron trifluoride-diethyl ether, followed by halogen exchange of the resulting fluorobismuthine 4a with brine.The (1)H NMR spectrum of compound 1a showed an unusually large downfield shift of a proton signal (δ 9.16), and X-ray structure analysis revealed that this unique shift was due to the anisotropic deshielding of the proton adjacent to the bismuth atom by the chlorine atom in close proximity.The bismuth centre of compound 1a was found to adopt a distorted pseudotrigonal bipyramidal geometry, probably through the formation of a hypervalent 3-centre 4-electron bond with the oxygen and chlorine atoms at apical positions.This is in marked contrast to the bismuthine 3a which has a pyramidal configuration characteristic of trivalent organobismuth compounds.A quite short Bi-O distance of compound 1a, compared with that of the bismuthine 3a, indicates that the introduction of an electronegative chlorine atom onto the bismuth atom enhances the Lewis acidity of the metal centre, leading to the pronounced intramolecular Bi-O interaction.
