Generation of Highly Enantioenriched Crystalline Products in Reversible Asymmetric Reactions with Racemic or Achiral Catalysts

Tsogoeva, Svetlana B.; Wei, Shengwei; Freund, Matthias; Mauksch, Michael

doi:10.1002/anie.200803877

Cited by 112 publications

(86 citation statements)

References 49 publications

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“…Tsogoeva, Mauksch and co-workers have reported enantioenrichment in solution for the enantiomer that forms the minor population in the solid phase during a reversible Mannich reaction. [11] The authors also conclude that surface-assisted racemization is active in that system. It was our aim to obtain quantitative data that could be numerically compared with the existing theoretical models.…”

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confidence: 92%

The Driving Mechanism Behind Attrition‐Enhanced Deracemization

et al. 2010

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Change of heart: A solution‐phase enantiomeric excess that has the handedness of the minor population of the solid phase is observed during grinding of a slurry of racemic conglomerate crystals. This excess is the driving force for a net flux of molecules from crystals of the minor handedness to crystals of the major handedness, thus explaining the complete deracemization of the solid phase (see picture: blue: S form, red: R form).

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confidence: 92%

The Driving Mechanism Behind Attrition‐Enhanced Deracemization

et al. 2010

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“…Application to the Mannich reaction has been described by Tsogoeva et al [71,72] and to an aldol condensation by Bolm et al [73]. Cuccia et al have described a rather broad application of attrition-induced deracemisation to a remarkable range of conglomerate crystals of intrinsically achiral organic molecules [69].…”

Section: Attrition-induced Deracemisationmentioning

confidence: 99%

How to Use Pasteur’s Tweezers

Kellogg

2015

Advances in Organic Crystal Chemistry

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Pasteur introduced two techniques to separate enantiomers. The common visual imagery is that of the first technique, which pertains to the use of tweezers to separate the mirror image crystals of a tartaric acid salt. A second method discovered thereafter, not restricted to the conglomerates necessary for the tweezer approach, is diastereomeric resolution. In this chapter, a short discussion is given of the basic principles of diastereomeric resolutions followed by short analysis of Dutch Resolution, a method based on the use of families of resolving agents. The role of specific nucleation inhibition is discussed. Attention is then turned to conglomerates. Preferential crystallisation is discussed briefly. Particular attention is paid to the discovery of near-equilibrium methods to separate (racemisable) conglomerates by employment of constant attrition of the growing crystals. This methodology has been extended to preparation of the chiral components of some major drugs, and the methodology has also been adapted to separation of nonracemisable conglomerates.

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“…8(a). Schematically, velocity may be represented as 14) with s c = (σ/∆µ) 2 . The supersaturation ∆µ, in fact, depends on the instantaneous monomer density.…”

Section: With Grindingmentioning

confidence: 99%

Selection of Crystal Chirality: Equilibrium or Nonequilibrium?

Saitō

Hyuga

2009

J. Phys. Soc. Jpn.

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To study the solution growth of crystals composed of chiral organic molecules, a spin-one Ising lattice gas model is proposed. The model turns out to be equivalent to the BlumeEmery-Griffiths model, which shows an equilibrium chiral symmetry breaking at low temperatures. The kinetic Monte Carlo simulation of crystal growth, however, demonstrates that Ostwald ripening is a very slow process with a characteristic time proportional to the system size: The dynamics is nonergodic. It is then argued that by incorporating grinding dynamics, homochirality is achieved in a short time, independent of the system size. Grinding limits cluster sizes to a certain range independent of system size and at the same time keeps the supersaturation so high that population numbers of average-sized clusters grow. If numbers of clusters for two types of enantiomers differ by chance, the difference is amplified exponentially and the system rapidly approaches the homochiral state. Relaxation time to the final homochiral state is determined by the average cluster size. We conclude that the system should be driven and kept in a nonequilibrium state to achieve homochirality.

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Generation of Highly Enantioenriched Crystalline Products in Reversible Asymmetric Reactions with Racemic or Achiral Catalysts

Cited by 112 publications

References 49 publications

The Driving Mechanism Behind Attrition‐Enhanced Deracemization

The Driving Mechanism Behind Attrition‐Enhanced Deracemization

How to Use Pasteur’s Tweezers

Selection of Crystal Chirality: Equilibrium or Nonequilibrium?

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