Structure of 2-(fluoromethyl)-2-[(p-tolylsulfinyl)methyl]oxirane

Fabrizi, Giancarlo; Fedeli, W.; Lamba, Doriano

doi:10.1107/s0108270191013574

Cited by 3 publications

(1 citation statement)

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“…The conformation around the central S(1)-X(3) bond is transoid, the torsional angle C(2)-C(3)-S(1)-C(30), defining the orientation of the phenyl ring and the fluoromethyl moiety, being 164.5(2)". The molecular geometry at S(l) conforms to that found for relatedp-tolylsulfinyl derivatives (17)(18)(19)(20)(21).…”

Section: Structural Assignmerltsmentioning

confidence: 77%

Stereoselective oxirane formation by reaction of diazomethane on 1-fluoro-3-[(4-methylphenyl)sulfinyl]-3-phenylpropan-2-one

Bravo¹,

Frigerio²,

Fronza³

et al. 1994

Can. J. Chem.

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F'IERFRANCESCO BRAVO, MASSIMO FRIGERIO, GIOVANNI FRONZA, VADIM SOLOSHONOK, FIORENZA VIANI, GIANCARLO CAVICCHIO, GIANCARLO FABRIZI, and DORIANO LAMBA. Can. J. Chem. 72, 1769Chem. 72, (1994. (2S,2'R,Rs)-2-(Fluoromethyl)-2-{[(4-methylphenyl)sulfinyl][phenyl]methyl)oxirane (4) was obtained in high chemical yield and with high diastereoselectivity by reacting diazomethane with pure (3R,Rs)-1-fluoro-3-[(4-methylphenyl)sulfinyl]-3-pheny1-propan-2-one (3), but also with its (3S,Rs)-3-diastereoisomer, in the latter case through inversion of the configuration at carbon 3. The corresponding methyl en01 ethers 6 were isolated as by-products. NMR experiments and molecular modelling calculations were performed in order to clarify the equilibria in solution and the preferred conformations of both ketones 3. Several variously substituted, sulfur-free tertiary a-(fluoromethy1)carbinols were obtained from the main reaction product (2S,2'R,Rs)-4 through appropriate elaborations of the sulfinyl group and of the oxirane ring. The structure of (2S,2'R,Rs) Le (2S,2'R,Rs)-2-(fluoromCthyl)-2-{[(4-mCthylphCnyl)sulfinyl][phCnyl]mCthyl)oxirane (4) fut obtenu avec d'excellents rendements chimiques et avec une diastCrCosClectivit6ClevCe en faisant rCagir du diazomkthane avec de la (3R,Rs)-1-fluoro-3-[(4-mCthylphCnyl)sulfinyl]-3-phCnylpropan-2-(3) pure ou sous la forme de mClange avec le diastCrCoisomkre (3S,Rs)-(3); dans ce dernier cas, la rCaction se fait par le biais d'une inversion de configuration au niveau du carbone 3. Les Cthers Cnoliques mCthyles correspondants (6) sont isolCs comme sous-produits. Des experiences de RMN et des calculs de modelage molCculaire ont Ct C exCcutCs pour clarifier les Cquilibres en solution et les conformations privilCgiCes des deux cCtones 3. On a prepare de nombreux a-(fluoromCthy1)carbinols tertiaires sans soufre et portant divers groupes fonctionnels par Claborations appropriCes du groupe fonctionnel sulfinyle et de l'anneau oxirane i partir du produit principal de la rCaction le (2S,2'R,Rs)-4. La structure du (2S,2'R,Rs)-4 a Ct C determinee par diffraction des rayons X du dCrivC aliphatique (2S,2'R,Rs)-l-bromo-3-fluoro-2'-{[(4-mCthylphCny1)sulfinyl I[phCnyl]mCthyl)propan-2-01 (7).[Traduit par la redaction]

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