Circular dichroism measurements in the VUV

1991 ◽  
Vol 56 (12) ◽  
pp. 3012-3024
Author(s):  
Aharon Gedanken
Keyword(s):  
Circular Dichroism ◽  
Absolute Configuration ◽  
Electronic States ◽  
Vibrational Structure ◽  
Excited Electronic States ◽  
Selection Rules ◽  
Absorption Studies ◽  
The Absolute ◽  
Circular Dichroïsm

The extension of circular dichroism measurements into the VUV region was motivated by the need to provide supplementary techniques to the absorption studies lacking rotational and vibrational structure. CD as one of these techniques is determined by selection rules which differ from those in absorption and thus enables the assignment of excited electronic states. Another application of VUVCD measurements is the use of correlation between the sign of the CD signal and the absolute configuration to formulate sector rules of chromophores absorbing only in the VUV. In this review we will present results obtained on our home-made instrument capable of measuring CD signal down to 150 nm. These applications of VUVCD will be demonstrated in systems such as the oxirane chromophore, the methylenecyclohexene chromophore and the amine chromophore. The role of singlet-triplet transitions and their contribution to CD and ORD will also be discussed.

Vibrational circular dichroism and single crystal X-Ray diffraction analyses of [Ir(bzq)2(phen)]+ (bzq = benzo[h]quinoline; phen = 1,10-phenanthroline): absolute configuration and role of CH–π interaction in molecular packing

2017 ◽  
Vol 46 (13) ◽  
pp. 4397-4402 ◽  
Author(s):  
Kazuyoshi Takimoto ◽  
Yutaka Watanabe ◽  
Shigeki Mori ◽  
Hisako Sato
Keyword(s):  
Circular Dichroism ◽  
Single Crystal ◽  
Absolute Configuration ◽  
Molecular Packing ◽  
Vibrational Circular Dichroism ◽  
X Ray Diffraction ◽  
X Ray ◽  
The Absolute ◽  
Circular Dichroïsm

The absolute configuration of a cationic iridium(iii) complex was determined in solution and solid by vibrational circular dichroism and X-ray diffraction analyses.

(-)-Strempeliopine, stereoselective total synthesis and the determination of absolute configuration

1986 ◽  
Vol 51 (8) ◽  
pp. 1731-1742 ◽  
Author(s):  
Josef Hájíček ◽  
Jan Trojánek
Keyword(s):  
Circular Dichroism ◽  
Total Synthesis ◽  
Absolute Configuration ◽  
Determination Of Absolute Configuration ◽  
Natural Base ◽  
The Absolute ◽  
Circular Dichroïsm

A synthesis of (±)-strempeliopine (II) is described, the key step of which is the stereoselective reductive rearrangement of 18-methylene-1,2-dehydroaspidospermidine (XI). The absolute configuration of the natural (-)-base II was determined as (2S, 7R, 20R, 21R) on the basis of its synthesis from (+)-18-methylenevincadifformine (XVII) the configuration of which was derived from a comparison of circular dichroism properties of bases with a β-anilinoacrylate chromophore. The biogenesis of the alkaloids of the schizozygane type is discussed.

scholarly journals Absolute Configuration Sensing of Chiral Aryl- and Aryloxy-Propionic Acids by Biphenyl Chiroptical Probes

Chemosensors ◽  
2021 ◽  
Vol 9 (7) ◽  
pp. 154
Author(s):  
Stefania Vergura ◽  
Stefano Orlando ◽  
Patrizia Scafato ◽  
Sandra Belviso ◽  
Stefano Superchi
Keyword(s):  
Circular Dichroism ◽  
Absolute Configuration ◽  
Optical Rotation ◽  
Environmental Pollutants ◽  
Red Shift ◽  
Electronic Circular Dichroism ◽  
Configuration Assignment ◽  
Clear Sign ◽  
The Absolute ◽  
Circular Dichroïsm

The 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.

Absolute configuration determination of theanti-head-to-head photocyclodimer of anthracene-2-carboxylic acid through cocrystallization withL-prolinol

2013 ◽  
Vol 69 (11) ◽  
pp. 1411-1413 ◽  
Author(s):  
Yuko Kawanami ◽  
Hidekazu Tanaka ◽  
Jun-ichi Mizoguchi ◽  
Nobuko Kanehisa ◽  
Gaku Fukuhara ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Circular Dichroism ◽  
Carboxylic Acid ◽  
Absolute Configuration ◽  
Void Space ◽  
Circular Dichroism Spectra ◽  
The Absolute ◽  
Circular Dichroïsm ◽  
Hydrogen Bonded

The absolute configuration has been established of the enantiopureanti-head-to-head cyclodimer of anthracene-2-carboxylic acid (AC) cocrystallized with L-propinol and dichloromethane [systematic name: (S)-2-(hydroxymethyl)pyrrolidin-1-ium (5R,6S,11R,12S)-8-carboxy-5,6,11,12-tetrahydro-5,12:6,11-bis([1,2]benzeno)dibenzo[a,e][8]annulene-2-carboxylate dichloromethane monosolvate], C5H12NO+·C30H19O4−·CH2Cl2. In the crystal structure, the AC dimer interacts with L-prolinol through a nine-membered hydrogen-bonded ring [R22(9)], while the dichloromethane molecule is incorporated to fill the void space. The absolute configuration determined in this study verifies a recent assignment made by comparing theoreticalversusexperimental circular dichroism spectra.

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