1,720,980 research outputs found
Biphenyl Chiroptical Probes for the Assignment of Absolute Configuration to Chiral Natural Products
No full textEnantioselective synthesis of the fungal metabolites colletochlorin A and colletorin A and their halogenated analogues
No full textAbsolute configuration sensing of chiral aryl-and aryloxy-propionic acids by biphenyl chiroptical probes
Full text linkThe absolute configuration of chiral 2-aryl and 2-aryloxy propionic acids, which are among the most common chiral environmental pollutants, has been readily and reliably established by either electronic circular dichroism spectroscopy or optical rotation measurements employing suitably designed 4,4′-disubstituted biphenyl probes. In fact, the 4,4′-biphenyl substitution gives rise to a red shift of the diagnostic electronic circular dichroism signal of the biphenyl A band employed for the configuration assignment, removing its overlap with other interfering dichroic bands and allowing its clear sign identification. The largest A band red shift, and thus the most reliable results, are obtained by employing as a probe the 4,4′-dinitro substituted biphenylazepine 3c. The method was applied to the absolute configuration assignment of 2-arylpropionic acids ibuprofen (1a), naproxen (1b), ketoprofen (1c) and flurbiprofen (1d), as well as to the 2-aryloxypropionic acids 2-phenoxypropionic acid (2a) and 2-naphthoxypropionic acid (2b). This approach, allowing us to reveal the sample’s absolute configuration by simple optical rotation measurements, is potentially applicable to online analyses of both the enantiomeric composition and absolute configuration of these chiral pollutants
Regio- And stereoselective intermolecular carbolithiation reactions
No full textThe inter-molecular carbolithiation of unfunctionalized and functionalized alkenes, followed by electrophile trapping, provides a versatile and useful tool for the construction of complex molecular systems, allowing the simultaneous creation of up to two novel carbon-carbon or carbon-heteroatom bonds. In this review a full overview oninter-molecular carbolithiation processes is reported, with a main focus on the chemo-, regio- and stereo-control of the reaction and on the strategies for asymmetric processes
A Vibrational Circular Dichroism Approach To The Determination Of The Absolute Configuration Of Flexible And Transparent Molecules: Fluorenone Ketals Of 1,N-Diols
No full textThe infrared absorption (IR) and vibrational circular dichroism (VCD) spectra for five ketal
molecules, three of which obtained from 1,2-diols and two from 1,3-diols, were recorded in the
mid-IR region. The spectra have been satisfactorily reproduced by DFT calculations, even with
not too large wavefunction basis sets, especially due to the low number of conformers to be
considered. The mobility of some moieties provides a recognizable signature. A characteristic
couplet of VCD bands attributed to normal modes involving the methine and a phenyl ring
bonded to the stereogenic carbon atom is evidenced for two ketals of the series as a signature
of the absolute configuration; due comparison with existing literature is made. A relation is
discussed of the present VCD data with the literature VCD data of simple alcohols and diols
Asymmetric synthesis of the natural products colletochlorin A and colletorin A and their halogenated synthetic analogues
No full text5,5,7,7-Tetrametyl-6,7-dihydro-5H-dibenzo[c,e]azepine
Full text link5,5,7,7-Tetrametyl-6,7-dihydro-5H-dibenzo[c,e]azepine has been synthesized as a possible pro-chiral (or tropos) unit for the construction of a chiral catalyst and as a molecular chirality sensor for the absolute configuration assignment by chiroptical spectroscopy. A straightforward synthetic strategy for the preparation of the title compound in high overall yield through sequential addition of the four methyl groups on benzylic positions has been described. A VT-NMR study was used to determine the rotational barrier of the aryl–aryl bond in this biphenylazepine, revealing its torsional flexibility at room temperature, which makes the biphenylazepine suitable as both a chirality probe and a tropos moiety in chiral ligands
Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
- …
