Optical purity, enantiomeric excess and the Horeau effect.

The optical purity of an enantiomeric mixture deduced from specific rotation measurements was found by Horeau to be different from its enantiomeric excess, which came to be known as the Horeau effect. This observation had important implications in the practical use of specific rotations and has led to investigations on homochiral and heterochiral aggregation processes. In this review, dedicated to the Horeau principle, the theoretical basis for the observance of the Horeau effect and a survey of the specific rotation studies investigating the Horeau effect are provided, and possible future investigations are suggested.

[1]  Ana G. Petrovic,et al.  Absolute Configuration and Conformation of (−)-R-t-Butylphenylphosphinoamidate: Chiroptical Spectroscopy and X-ray Analysis , 2020, The Journal of organic chemistry.

[2]  T. Roisnel,et al.  Persistent Organic Room-Temperature Phosphorescence in Cyclohexane-trans-1,2- Bisphthalimide Derivatives: the Dramatic Impact of Heterochiral vs. Homochiral Interactions. , 2020, The journal of physical chemistry letters.

[3]  G. K. Boulogiannis,et al.  Gas-phase optical activity measurements using a compact cavity ringdown polarimeter , 2020, Laser Physics.

[4]  K. Michal Pietrusiewicz,et al.  A General Phenomenon of Spontaneous Amplification of Optical Purity under Achiral Chromatographic Conditions , 2019, Symmetry.

[5]  J. Yuasa,et al.  Competing Allosteric Mechanisms for Coordination-Directed Conformational Changes of Chiral Stacking Structures with Aromatic Rings. , 2019, Inorganic chemistry.

[6]  P. Vaccaro,et al.  Dispersive Optical Activity of (R)-Methylene Norbornene: Intrinsic Response and Solvation Effects. , 2017, The journal of physical chemistry. A.

[7]  P. Polavarapu.  Chiroptical Spectroscopy: Fundamentals and Applications , 2016 .

[8]  A. Kaczor,et al.  Aggregation-Induced Resonance Raman Optical Activity (AIRROA): A New Mechanism for Chirality Enhancement. , 2016, The journal of physical chemistry. B.

[9]  P. Polavarapu,et al.  Specific Optical Rotations and the Horeau Effect. , 2016, Chirality.

[10]  P. Polavarapu,et al.  Wavelength resolved specific optical rotations and homochiral equilibria. , 2015, Physical chemistry chemical physics : PCCP.

[11]  V. Villari,et al.  Role of the hydrogen-bond in porphyrin J-aggregates , 2012 .

[12]  J. Autschbach.  AB Initio Electronic Circular Dichroism and Optical Rotatory Dispersion: From Organic Molecules to Transition Metal Complexes , 2012 .

[13]  Alicija Bilinska.  Synthesis of chiral bicyclo(3.3.1)nonane derivative as ionic liquid and using it for asymmetric Michael's addition reaction , 2012 .

[14]  V. Soloshonok,et al.  Remarkable amplification of the self-disproportionation of enantiomers on achiral-phase chromatography columns. , 2006, Angewandte Chemie.

[15]  P. Stephens,et al.  Determination of molecular structure in solution using vibrational circular dichroism spectroscopy: the supramolecular tetramer of S-2,2'-dimethyl-biphenyl-6,6'-dicarboxylic acid. , 2005, Journal of the American Chemical Society.

[16]  M. Morbidelli,et al.  Determination of the Dimerization Equilibrium Constants of Omeprazole and Pirkle's Alcohol through Optical‐Rotation Measurements , 2004 .

[17]  Ana G. Petrovic,et al.  Intrinsic rotation and molecular structure. , 2003, Chirality.

[18]  M. Morbidelli,et al.  Measurement of the Dimerization Equilibrium Constants of Enantiomers , 2002 .

[19]  J. Chaires,et al.  Allosteric, chiral-selective drug binding to DNA. , 2000, Proceedings of the National Academy of Sciences of the United States of America.

[20]  A. Solladié-Cavallo,et al.  Hydroxypinanone: Solute/solute interactions and non-linear chiroptical properties , 1997 .

[21]  P. Polavarapu.  AB INITIO MOLECULAR OPTICAL ROTATIONS AND ABSOLUTE CONFIGURATIONS , 1997 .

[22]  M. Ács.  Chiral Recognition in the Light of Molecular Associations , 1991 .

[23]  Y. Kyōgoku,et al.  Intermolecular Hydrogen Bonding of Enantiomers of Pantolactone Studied by Infrared and 1H-NMR Spectroscopy , 1985 .

[24]  A. Horeau,et al.  Interactions diastereoisomeres d'antipodes en phase liquide , 1974 .

[25]  A. Horeau.  Interactions d'enantiomeres en solution ; influence sur le pouvoir rotatoire : Purete optique et purete enantiomerique. , 1969 .

[26]  R. K. Hill,et al.  Absolute configuration of a dissymmetric spiran , 1968 .

[27]  Ernest L. Eliel,et al.  Stereochemistry of Organic Compounds , 1962 .