The steric effect of a trifluoromethyl group.

Nagai, Takabumi; Nishioka, Goro; Koyama, Mayumi; Andõ, Akira; Miki, Takuichi; Kumadaki, Itsumaro

doi:10.1248/cpb.39.233

Cited by 29 publications

(8 citation statements)

References 2 publications

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“…This effect is mostly due to the steric factor of the CF 3 group, which hinders the reaction at the nitrogen atom. It is known that the Charton's steric parameter of the CF 3 group ( ν = 0.91) is similar to that of the sec ‐butyl ( ν = 1.02) or cyclohexyl ( ν = 0.87) group …”

Section: Resultsmentioning

confidence: 65%

Quinoline and ferrocene conjugates: Synthesis, computational study and biological evaluations

Maračić

Lapić

Djaković

et al. 2018

Applied Organom Chemis

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Novel O-alkylated quinoline and N-alkylated 4-quinolone derivatives attached to the ferrocene moiety through 4,1-(7a-d, 8a-d and 12a-d) and 1,4-disubstituted (9a, 9b, 10a and 10b) 1,2,3-triazole moiety were synthesized. The observed regioselectivity of O-vs. N-alkylation was explored by the use of NMR and computational techniques. Among the N-alkylated derivatives, the quinolone-ferrocene conjugate 9a displayed marked activities against chronic myeloid leukemia in blast crisis (K562) and Burkitt lymphoma (Raji). The 6-chloroquinolone-ferrocene conjugate 12c, with selective inhibitory activity on Raji cells and no cytostatic effect on normal MDCK1 cells was highlighted as the most promising anticancer organometallic complex in a group of O-alkylated quinolines.

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Section: Resultsmentioning

confidence: 65%

Quinoline and ferrocene conjugates: Synthesis, computational study and biological evaluations

Maračić

Lapić

Djaković

et al. 2018

Applied Organom Chemis

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“…The most compelling evidence for this estimation comes from measurements of rotational barriers in 1,1’-disubstituted biphenyls along the biphenyl axis and the results are suggestive of a −CF 3 group imposing steric restrictions equivalent to those of a −CH(CH 3 ) 2 group 39–41. In order to assess whether the size of the pendant group at the 5-position of neuraminic acid is the key determinant of decreased adhesion, compounds 6a and 7a were used as controls for 3a and 5 .…”

Section: Resultsmentioning

confidence: 99%

Modulation of Cellular Adhesion by Glycoengineering

Dafik¹,

d’Alarcao²,

Kumar³

2010

J. Med. Chem.

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Aberrant glycosylation of lipid and protein molecules on cellular surfaces is responsible for many of the pathophysiological events in tumor progression and metastasis. Sialic acids in particular, are overexpressed on the glycocalyx of malignant tumor cells and sialic acid-mediated cell adhesion is required for metastasis. We report here that replacement of sialic acids on cell surfaces with fluorinated congeners dramatically decreases cell adhesion to E-and P-selectin-coated surfaces.Comparison of adhesion of fluorinated cells with those modified with non-fluorinated analogues suggests that both reduce binding of the modified sialosides to their cognate lectins to a similar extent on a per molecule basis. The overall reduction in cell adhesion results from greater cell surface presentation of the fluorinated congeners. This work suggests an avenue for inhibition of metastasis by administration of small molecules, and concomitant non-invasive imaging of tumor cells by 19 F MRI before they are visible by other means.

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“…The diastereoselectivity of nucleophilic addition to carbonyl groups in cyclic (and acyclic) systems depends on the size of the incoming nucleophile and the steric environment of the carbonyl group. Both ab initio calculations and empirical studies suggest that the trifluoromethyl group is comparable in size to an isopropyl group using a half-sphere approximation . Therefore, a significant degree of diastereoselectivity in the trifluoromethylation of carbonyl groups with adjacent chiral carbon atoms might be expected.…”

Section: Resultsmentioning

confidence: 99%

Reaction of (Trifluoromethyl)trimethylsilane with Oxazolidin-5-ones: Synthesis of Peptidic and Nonpeptidic Trifluoromethyl Ketones

Walter¹,

Adlington²,

Baldwin³

et al. 1998

J. Org. Chem.

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(Trifluoromethyl)trimethylsilane (TMS-CF3, the Ruppert Reagent) reacts with a variety of amino acid derived N-substituted oxazolidin-5-ones in excellent yields. Mild acid hydrolysis of adducts with electron-releasing substituents at C-2 affords N-substituted α-amino trifluoromethyl ketones (TFMKs). N-CBZ-protected α-amino TFMKs are converted into hitherto unreported hydrochloride salts of α-amino TFMKs by hydrogenolysis. Coupling with amino acid fluorides gives access to peptidic TFMKs which are of utility as protease inhibitors.

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The steric effect of a trifluoromethyl group.

Cited by 29 publications

References 2 publications

Quinoline and ferrocene conjugates: Synthesis, computational study and biological evaluations

Quinoline and ferrocene conjugates: Synthesis, computational study and biological evaluations

Modulation of Cellular Adhesion by Glycoengineering

Reaction of (Trifluoromethyl)trimethylsilane with Oxazolidin-5-ones: Synthesis of Peptidic and Nonpeptidic Trifluoromethyl Ketones

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