Preparation of enantiopure 1-isopentyl-3-methyl-3-phospholene 1-oxide via the formation of diastereomeric complexes

2018 ◽  
Vol 29 (1) ◽  
pp. e21411
Author(s):  
Péter Bagi ◽  
Kinga Juhász ◽  
Mihály Kállay ◽  
Dóra Hessz ◽  
Miklós Kubinyi ◽  
...  
Keyword(s):  
Diastereomeric Complexes

scholarly journals Photochemical R2PI study of chirality and intermolecular forces in supersonic beam

2001 ◽  
Vol 3 (4) ◽  
pp. 223-227 ◽  
Author(s):  
A. Giardini Guidoni ◽  
S. Piccirillo ◽  
D. Scuderi ◽  
M. Satta ◽  
T. M. Di Palma ◽  
...  
Keyword(s):  
Excited States ◽  
Molecular Beam ◽  
Intermolecular Forces ◽  
Excitation Spectra ◽  
Supersonic Molecular Beam ◽  
Spectral Shifts ◽  
Band Origin ◽  
Solvent Molecules ◽  
The One ◽  
Diastereomeric Complexes

One and two-color, mass selected R2PI spectra of theS1←S0transitions in the bare(+)-(R)- 1-phenyl-1-ethanol(ER) and its complexes with different solvent molecules (solv) (-)-(R)-2-butanol(BR) or(+)-(S)-2-butanol(BS), (—)-(R)-2-pentanol (TR) or(+)-(S)-2-pentanol(TS) and(-)-(R)-2-butylamine(AR) or(+)-(S)-2-butylamine(AS), have been recorded after a supersonic molecular beam expansion. The one-color R2PI excitation spectra of the diastereomeric complexes are characterized by significant shifts of their band origin relative to that of bareER. The extent and the direction of these spectral shifts are found to depend upon the structure and the configuration ofsolvand are attributed to different short-range interactions in the ground and excited states of the complexes. In analogy with other diastereomeric complexes, the phenomenological binding energy of the homochiral cluster is found to be greater than that of the heterochiral one. Preliminary measurements of excitation spectrum of(+)-(R)-1-Indanol(IR) is also reported.

The Theoretical Basis for Assignment by NMR

2015 ◽  
Author(s):  
Josi M. Seco ◽  
Emilio Quiqoa ◽  
Ricardo Riguera
Keyword(s):  
Absolute Configuration ◽  
Chiral Auxiliary ◽  
Primary Amines ◽  
Primary Alcohols ◽  
Chiral Reagent ◽  
Chiral Compounds ◽  
Configurational Assignment ◽  
Derivatizing Agent ◽  
Chiral Derivatizing Agent ◽  
Diastereomeric Complexes

The nuclear magnetic resonance (NMR) spectra of two enantiomers are identical. Thus, the first step in using NMR to distinguish between two enantiomers should be to produce different spectra that eventually can be associated with their different stereochemistry (i.e., the assignment of their absolute configuration). Therefore, it is necessary to introduce a chiral reagent in the NMR media. There are two ways to address this problem. One is to use a chiral solvent, or a chiral agent, that combines with each enantiomer of the substrate to produce diastereomeric complexes/associations that lead to different spectra. This is the so-called chiral solvating agent (CSA) approach; it will not be further discussed here [33–34]. The second approach is to use a chiral auxiliary reagent [13–15] (i.e., a chiral derivatizing agent; CDA) that bonds to the substrate by a covalent linkage. Thus, in the most general method, the two enantiomers of the auxiliary CDA react separately with the substrate, giving two diastereomeric derivatives whose spectral differences carry information that can be associated with their stereochemistry. The CDA method that employs arylalcoxyacetic acids as auxiliaries is the most frequently used. It can be applied to a number of monofunctionals [14–15] (secondary alcohols [35–43], primary alcohols [44–46], aldehyde [47] and ketone cyanohydrins [48–49], thiols [50–51], primary amines [52–56], and carboxylic acids [57–58]), difunctional [13] (sec/sec-1,2-diols [59–61], sec/sec-1,2-amino alcohols [62], prim/sec-1,2-diols [63–65], prim/sec-1,2-aminoalcohols, and sec/prim-1,2-aminoalcohols [66–68]), and trifunctional (prim/sec/sec-1,2,3-triols [13, 69–70]) chiral compounds. Its scope and limitations are well established, and its theoretical foundations are well known, making it a reliable tool for configurational assignment. Figure 1.1 shows a summary of the steps to be followed for the assignment of absolute configuration of a chiral compound with just one asymmetric carbon and with substituents that, for simplicity, are assumed to resonate as singlets. Step 1 (Figure 1.1a): A substrate of unknown configuration (?) is separately derivatized with the two enantiomers of a chiral auxiliary reagent, (R)-Aux and (S)-Aux, producing two diastereomeric derivatives.

Spectroscopic Discrimination of Diastereomeric Complexes Involving an Axially Chiral Receptor

ChemPhysChem ◽  
2017 ◽  
Vol 18 (18) ◽  
pp. 2475-2481 ◽  
Author(s):  
Antonello Filippi ◽  
Caterina Fraschetti ◽  
Laura Guarcini ◽  
Costantino Zazza ◽  
Tadashi Ema ◽  
...  
Keyword(s):  
Axially Chiral ◽  
Diastereomeric Complexes

A comparative study of diastereomeric complexes formed by a prochiral substrate and three structurally analogous chiral molecules on Pt(111)

2016 ◽  
Vol 646 ◽  
pp. 13-18 ◽  
Author(s):  
Jean-Christian Lemay ◽  
Yi Dong ◽  
Michael N. Groves ◽  
Vincent Demers-Carpentier ◽  
Guillaume Goubert ◽  
...  
Keyword(s):  
Comparative Study ◽  
Chiral Molecules ◽  
Diastereomeric Complexes

Chiral recognition of amino acid derivatives: an NMR investigation of the selector and the diastereomeric complexes

1989 ◽  
Vol 54 (3) ◽  
pp. 684-688 ◽  
Author(s):  
Alberto Spisni ◽  
Roberto Corradini ◽  
Rosangela Marchelli ◽  
Arnaldo Dossena
Keyword(s):  
Amino Acid ◽  
Chiral Recognition ◽  
Amino Acid Derivatives ◽  
Diastereomeric Complexes

scholarly journals Enantioselective supramolecular devices in the gas phase. Resorcin[4]arene as a model system

2012 ◽  
Vol 8 ◽  
pp. 539-550 ◽  
Author(s):  
Caterina Fraschetti ◽  
Matthias C Letzel ◽  
Antonello Filippi ◽  
Maurizio Speranza ◽  
Jochen Mattay
Keyword(s):  
Gas Phase ◽  
Chiral Recognition ◽  
Experimental Approach ◽  
Biologically Active ◽  
Computational Techniques ◽  
Ligand Displacement ◽  
Artificial Receptor ◽  
Ion Molecule Complexes ◽  
Supramolecular Devices ◽  
Diastereomeric Complexes

This review describes the state-of-art in the field of the gas-phase reactivity of diastereomeric complexes formed between a chiral artificial receptor and a biologically active molecule. The presented experimental approach is a ligand-displacement reaction carried out in a nano ESI-FT-ICR instrument, supported by a thermodynamic MS-study and molecular-mechanics and molecular-dynamics (MM/MD) computational techniques. The noncovalent ion–molecule complexes are ideal for the study of chiral recognition in the absence of complicating solvent and counterion effects.

Chlorine Para-Substitution of 1-Phenylethanol: Resonant Photoionization Spectroscopy and Quantum Chemical Calculations of Hydrated and Diastereomeric Complexes

2016 ◽  
Vol 120 (27) ◽  
pp. 5023-5031 ◽  
Author(s):  
Flaminia Rondino ◽  
Mauro Satta ◽  
Susanna Piccirillo ◽  
Alessandra Ciavardini ◽  
Anna Giardini ◽  
...  
Keyword(s):  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Diastereomeric Complexes

Relative Abundances of Surface Diastereomeric Complexes Formed by Two Chiral Modifiers That Differ by a Methyl Group

ACS Catalysis ◽  
2020 ◽  
Vol 10 (5) ◽  
pp. 3034-3041
Author(s):  
Jean-Christian Lemay ◽  
Yi Dong ◽  
Vincent Albert ◽  
Monica Inouye ◽  
Michael N. Groves ◽  
...  
Keyword(s):  
Methyl Group ◽  
Relative Abundances ◽  
Diastereomeric Complexes
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