Preparation and properties of chiral fluoroorganic compounds

Bravo, Pierfrancesco; Resnati, G.

doi:10.1016/s0957-4166(00)82374-5

Cited by 224 publications

(35 citation statements)

References 258 publications

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“…[3] The interest in chiral fluorinated compounds is not new but has increased in recent years. [4,5] Apart from their use in asymmetric synthesis, some fluorinated organic compounds exhibit peculiar and sometimes unexpected chiroptical properties, which have been discussed and rationalized. [6][7][8][9][10][11] The second context mentioned above is crystal engineering, for which the characteristic noncovalent inter-transfer (CT) character, as demonstrated by the CT metric index Γ NTO .…”

Section: Introductionmentioning

confidence: 99%

Circular Dichroism and TDDFT Investigation of Chiral Fluorinated Aryl Benzyl Sulfoxides

et al. 2015

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A series of ten chiral aryl benzyl sulfoxides with perfluorinated aryl or benzyl rings, obtained by enantioselective oxidation of sulfides, has been investigated by means of electronic circular dichroism (ECD) spectroscopy and time-dependent DFT (TDDFT) calculations. The (per)fluorination of the aromatic rings has a large impact on the conformer population, the molecular orbitals shape, and the character of electronic transitions. In this series, the transition responsible for the “sulfoxide primary” CD band has a large charge transfer (CT) character, as demonstrated by the CT metric index ΓNTO. As a consequence, global DFT hybrids such as B3LYP are largely inaccurate in the prediction of excited states; nevertheless, a correct simulation of CD spectra may be achieved by using range-separated functionals such as CAM-B3LYP. The use of the empirical Mislow's rule for assigning the absolute configuration is strongly discouraged for this class of compounds

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Section: Introductionmentioning

confidence: 99%

Circular Dichroism and TDDFT Investigation of Chiral Fluorinated Aryl Benzyl Sulfoxides

et al. 2015

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“…35 In the past, most methods of obtaining chiral tri-fluorinated compounds of this type 25 revolved around the resolution of racemates or enantioselectively adding the CF 3 moiety to a chiral compound. 36 This moiety has a very strong effect on the electron density of the olefinic bond, more so than a carboxylic or ether group would. 37 The asymmetric hydrogenation of trifluoromethylated alkenes has 30 been attempted with (R)-BINAP-Ru catalysts with results varying from racemic to 83% ee.…”

Section: Trifluoromethylated Olefinsmentioning

confidence: 99%

Iridium catalysis: application of asymmetric reductive hydrogenation

Cadu

Andersson

2013

Dalton Trans.

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PostprintThis is the accepted version of a paper published in Dalton Transactions. This paper has been peerreviewed but does not include the final publisher proof-corrections or journal pagination. Iridium, despite being one of the least abundant transition metals, has known several uses. N,P-ligated 5 iridium catalysts are used to perform many highly selective reactions. These methodologies have been developed extensively over the past 15 years. More recently, the application of iridium N,P catalysts in asymmetric hydrogenation has been a focus, to find novel applications and to expand on their current synthetic utility. The aim of this perspective is to highlight the advances made by the Andersson group.

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“…119.5 (7) O ( fluoro-substituted organic molecules (Bravo & Resnati, 1990;Cavicchio, Marchetti, Arnone, Bravo & Viani, 1990), an efficient transfer of chirality from S to the central C atom was observed when (S)-(-)-1-fluoro-3-(p-tolylsulfinyl)propan-2-one (1) was reacted with diazomethane (Cavicchio, Bravo, Marchetti & Zappal~, 1991). Here we report on the crystal and molecular structure of 2-(fluoromethyl)-2-[(p-tolylsulfinyl)methyl]oxirane (2), obtained in good yield and with high diastereomeric excess, in order to determine the absolute configuration of the new chiral centre at C(2).…”

Section: (3) O(2)---s(1)--c(22) 1079 (3) C(21)---s(1)--c(22) 963 (3mentioning

confidence: 99%