Separation of an Enantiomorph and Its Racemate by Distillation: Strong Chiral Recognizing Ability of Trifluorolactates

Katagiri, Toshimasa; Yoda, Chika; Furuhashi, Keizo; Ueki, Katsuyuki; Kubota, Toshio

doi:10.1246/cl.1996.115

Cited by 76 publications

(72 citation statements)

References 5 publications

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“…For instance, purification of an enantiomerically enriched sample of 1 of 75% ee to optically pure (S)-1 form via conventional crystallization technique, requires several consecutive re-crystallizations furnishing an enantiomerically pure compound in about 60% yield [7]. On the other hand sublimation of sample of 1 of 79.4% ee over 25 min resulted in optically pure (S)-1, which was collected with 81.7% yield.…”

Section: Resultsmentioning

confidence: 99%

Self-disproportionation of enantiomers of isopropyl 3,3,3-(trifluoro)lactate via sublimation: Sublimation rates vs. enantiomeric composition

Yasumoto¹,

Ueki²,

Ono³

et al. 2010

Journal of Fluorine Chemistry

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Section: Resultsmentioning

confidence: 99%

Self-disproportionation of enantiomers of isopropyl 3,3,3-(trifluoro)lactate via sublimation: Sublimation rates vs. enantiomeric composition

Yasumoto¹,

Ueki²,

Ono³

et al. 2010

Journal of Fluorine Chemistry

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“…In the case of trifluorolactate, the alteration of the boiling point of the mixtures of the enantiomers depending on their enantiomeric excess could be attributed to this resolution phenomenon. Moreover, a contribution of hydrogen bonding in the liquid state was also suggested by an IR spectroscopic result [3].…”

Section: Introductionmentioning

confidence: 82%

“…To date, so many reports on such discrimination have been reported but denied [1]. To the author's knowledge, there have been only two examples: trifluorolactate (1) [3] and N-trifluoroacetyl valine methyl ester (2) [4]. It is noteworthy that both of these compounds have btrifluorinated proton donating groups.…”

Section: Introductionmentioning

confidence: 99%

Discrimination of enantiomeric excess of optically active trifluorolactate by distillation: Evidence for a multi-center hydrogen bonding network in the liquid state

Katagiri

Takahashi

Tsuboi

et al. 2010

Journal of Fluorine Chemistry

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“…For the purposes of the definitions that follow, clearly the pot residue can be taken as the more stable state and the vapor/distillate as the less stable. For one system [31], behavior in many respects resembles that of a racemic compound (an ep of lower stability with respect to both the pure enantiomer and the racemate) whilst inverted behavior also seems evident for another system [32] (an ep of higher stability with respect to both the pure enantiomer and the racemate). SDE antiomer self-disproportionation on achiral chromatography (ESDAC) [33][34][35][36][37], bears some similarity to the aforementioned phase transitions, though some distinctions are apparent.…”

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confidence: 99%

Suggested New Terms for Describing Chiral States and the State-Dependent Behavior of Chiral Systems

Klika¹

2012

IJOC

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Deficiencies in the terminology used to describe chiral systems exist for behaviors under various processes and thus a more general, robust terminology is considered. For example, the descriptions for characterizing melting point, solubility, and recrystallization behaviors were adopted well before it was realized that perturbation of the enantiomeric composition (ec) due to self-disproportionation could be effected by processes other than recrystallization such as sublimation, chromatography over achiral substrates, and even distillation. Thus, an endeavor has been made to address the question of universally describing behaviors under processes that effect, or are dependent on, the ec. The main terms that have been defined with respect to behavior are homomate (analogous to a conglomerate), heteromate, bimate (analogous to a racemic compound), and unimate (analogous to a solid solution) and they apply to melting point, solubility, recrystallization, sublimation, distillation, and chromatographic processes. Additionally, suggestions for improving the terminology for describing the states of chiral systems are also considered and the defined terms are: holemate (hol, ec = 100%), scalemate (scl, 50% < ec < 100%), and equimate (eqm, ec = 50%).Keywords: Stereochemistry; Terminology; Chirality; State-Dependent Behavior; Conglomerate; Racemate A clear consensus for describing chiral systems, both for processes, behaviors, and for the general state of systems, does not seem to be in effect despite the enormous amount of study devoted to chiral systems and their associated behaviors ever since the seminal experiments of Pasteur into the relationships between the crystalline state and chemical composition and their relation to optical rotation (OR) [1,2]-thus consequently the very embodiment of chirality and the subsequent inferences for homochirality, not to mention of course, the very report of the spontaneous resolution of a conglomerate itself [3]. Invariably, whatever particular description is adopted encounters objection from one quarter or another and hence the obvious question, though rhetorical in nature, is, what is the origin of the confusion and ambiguity that exists? In part, confusion and ambiguity arise because authors may be, for example, be referring to a single molecule or type of molecule or, on the other hand, an aggregation of molecules or a real sample analysis without taking due care to be precise in their meaning and simply assuming that the context of the discussion is sufficient to effect a distinction. Another source of confusion is the fact that as new frontiers were explored or developed, the terminology failed to keep pace and terms were simply borrowed out of convenience. There is no better example of this than the term homochiral 1 [4][5][6]. Thus it is the intention of this report to help alleviate some of the deficiencies that have developed in the terminology in use with respect to chiral systems, especially since the systems that give rise to varying chiral behaviors have risen...

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Separation of an Enantiomorph and Its Racemate by Distillation: Strong Chiral Recognizing Ability of Trifluorolactates

Cited by 76 publications

References 5 publications

Self-disproportionation of enantiomers of isopropyl 3,3,3-(trifluoro)lactate via sublimation: Sublimation rates vs. enantiomeric composition

Self-disproportionation of enantiomers of isopropyl 3,3,3-(trifluoro)lactate via sublimation: Sublimation rates vs. enantiomeric composition

Discrimination of enantiomeric excess of optically active trifluorolactate by distillation: Evidence for a multi-center hydrogen bonding network in the liquid state

Suggested New Terms for Describing Chiral States and the State-Dependent Behavior of Chiral Systems

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