Chiral self-recognition in the gas phase: the case of glycidol dimers

Borho, Nicole; Häber, Thomas; Suhm, Martin A.

doi:10.1039/b102382a

Cited by 48 publications

(53 citation statements)

References 19 publications

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“…The most stable monomer conformation ((S)-gÀg + ) and the most stable dimer structures (RS (C i ) and SS (C 2 ), activated addition type) are shown (adapted from ref. [114]). …”

Section: -Naphthyl-1-ethanol Complexes With Secondary Alcoholsmentioning

confidence: 93%

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Chirality Recognition between Neutral Molecules in the Gas Phase

2008

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Noncovalent interactions are particularly intriguing when they involve chiral molecules, because the interactions change in a subtle way upon replacing one of the partners by its mirror image. The resulting phenomena involving chirality recognition are relevant in the biosphere, in organic synthesis, and in polymer design. They may be classified according to the permanent or transient chirality of the interacting partners, leading to chirality discrimination, chirality induction, and chirality synchronization processes. For small molecules, high-level quantum chemical calculations for such processes are feasible. To provide reliable connections between theory and experiment, such phenomena are best studied in vacuum isolation at low temperature, using rotational, vibrational, electronic, and photoionization spectroscopy. We review these techniques and the results which have become available in recent years, with special emphasis on dimers of permanently chiral molecules and on the influence of conformational flexibility. Analogies between the microscopic mechanisms and macroscopic phenomena and between intra- and intermolecular cases are drawn.

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“…The most stable monomer conformation ((S)-gÀg + ) and the most stable dimer structures (RS (C i ) and SS (C 2 ), activated addition type) are shown (adapted from ref. [114]). …”

Section: -Naphthyl-1-ethanol Complexes With Secondary Alcoholsmentioning

confidence: 93%

“…[114,115] Glycidol consists of a rigid oxirane ring with a methanol substituent, locked by a hydrogen bond in a double gauche geometry. The restricted conformational flexibility minimizes spectral congestion.…”

Section: Glycidol Dimermentioning

confidence: 99%

Chirality Recognition between Neutral Molecules in the Gas Phase

2008

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“…[31] In the present case, the two dominant conformations of the Gly monomer are present with an intensity ratio of 4:1 at room temperature. In the previous jet-cooled FTIR study, [32] it was noted that the intensity ratio of these two monomeric conformers further increases in a helium jet expansion, indicating that the interconversion barrier separating these two monomeric conformers can be overcome. One may therefore expect to overcome such a barrier in a Neon expansion in the present case.…”

Section: ð þ ð1þmentioning

confidence: 95%

Chirality Recognition in the Glycidol⋅⋅⋅Propylene Oxide Complex: A Rotational Spectroscopic Study

Thomas

Sunahori

Borho

et al. 2011

Chemistry A European J

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Chirality recognition in the hydrogen-bonded glycidol···propylene oxide complex has been studied by using rotational spectroscopy and ab initio calculations. An extensive conformational search has been performed for this binary adduct at the MP2/6-311++G(d,p) level of theory and a total of 28 homo- and heterochiral conformers were identified. The eight binary conformers, built of the two dominant glycidol monomeric conformers, g-G+ and g+G-, were predicted to be the most stable ones. Jet-cooled rotational spectra of six out of the eight conformers were observed and unambiguously assigned for the first time. The experimental stability ordering has been obtained and compared with the ab initio predictions. The relative stability of the two dominant glycidol monomeric conformers is reversed in some cases when binding to propylene oxide. The contributions of monomeric energy, deformation energy, and binary intermolecular interaction energy to the relative stability of the binary conformers are discussed.

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“…King and Howard reported a microwave study of the heterochiral dimer of 2-butanol [6]. Suhm et al have examined the dimers of glycidol and clusters of lactate derivatives by means of FTIR spectroscopy [7,8]. Beu and Buck found evidence of the presence of different chiral isomers in the IR-spectra of hydrazine clusters [9].…”

Section: Introductionmentioning

confidence: 97%

Dimers of 1,8a-Dihydro-1,8-Naphthyridine Derivatives as Models of Chiral Self-Recognition

2005

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A theoretical study of the dimer formation of chiral 1,8a-dihydro-1,8-naphthyridine derivatives has been carried out by means of DFT calculations. In the cases treated, the heterochiral dimers (RS or SR) are always more stable than the homochiral ones (RR or SS). Two possible proton transfer processes have been studied, the concerted and the non-concerted ones. The non-concerted TS corresponds to a true TS while the concerted one presents two imaginary frequencies. The geometrical characteristics of the hydrogen bonds in all the structures calculated have been correlated using the Steiner-Limbach model.

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Chiral self-recognition in the gas phase: the case of glycidol dimers

Cited by 48 publications

References 19 publications

Chirality Recognition between Neutral Molecules in the Gas Phase

Chirality Recognition between Neutral Molecules in the Gas Phase

Chirality Recognition in the Glycidol⋅⋅⋅Propylene Oxide Complex: A Rotational Spectroscopic Study

Dimers of 1,8a-Dihydro-1,8-Naphthyridine Derivatives as Models of Chiral Self-Recognition

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