Chirally and chemically reversible Strecker reaction

Machida, Yutaro; Tanaka, Yuzuru; Masuda, Yoshio; Kimura, Aya Hirata; Kawasaki, Tsuneomi

doi:10.1039/d3sc00359k

Cited by 7 publications

(2 citation statements)

References 60 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since Pasteur’s finding of spontaneous resolution of tartrates, developing strategies that manipulate the solid-state or crystalline chiroptical materials have attracted persistent interests. − In contrast to the chiral counterparts in solutions, solid chiroptical materials show feasible processability toward advanced applications and functions beyond the determination of absolute configuration, especially in thin-film or device-related diodes or transistors. − Precise and rational control over chirality and chiroptical properties of crystals or solids remains considerable challenges ascribed to the poor understanding of structure–property correlation. , It is complicated considering the molecular conformation and supramolecular-level molecular stacking . Formation of enantiorich or pure aggregates is reinforced by the crystallization-induced chiral amplification with chiral source from inherent molecular chirality, external fields, or in spontaneous way. − Materials that could undergo spontaneous formation or solution during crystallization in racemates are defined as conglomerate crystals, which have been recognized as a widely existing behavior. − Conglomerate crystallization phenomenon contains the processes of both symmetry breaking and chiral amplification. − Though chemists are familiar with this phenomenon, its potentials in asymmetric synthesis and especially functional chiroptical materials are underdeveloped and rarely recognized. Statistic data from Cambridge Structural Database suggest that about 10% crystals have conglomerate behaviors, which potentially is an enormous candidate library for diversified chiroptical usages. − The state-of-art exploration with respect to chiroptical materials is, however, pretty rare. , …”

Section: Introductionmentioning

confidence: 99%

Phosphorescent Thermal Chiroptical Switch Built through Highly Efficient Chiral Recognition and Amplification

Wang,

Hao,

Xing

2023

Chem. Mater.

View full text Add to dashboard Cite

Solid and crystalline chiroptical materials show advanced applications in optoelectronic devices, such as polarized photodetectors. However, rational control of the solid-state chirality as well as the extension of chiral optic functionalities remains a great challenge. Here, we show the introduction of a chiral molecular seed to control the homochirality, luminescence, and chiral optics of conglomerate crystals with half-propeller and propeller chirality. A chiral bromo-naphthalimide derivative acts as a chiral seed to control the chirality of a series of conglomerate crystals through highly efficient chiral recognition and amplification. In addition, the molecular seed synergistically triggers the emergence of room-temperature phosphorescence with a critical doping ratio as low as 0.01 mol %. It facilitates the generation of circularly polarized phosphorescence that can be switched on and off by a thermal treatment in the crystalline state. This unprecedented phosphorescent thermal chiroptical switch has excellent thermal repeatability that will have potential in smart devices for display and sensing.

show abstract

Section: Introductionmentioning

confidence: 99%

Phosphorescent Thermal Chiroptical Switch Built through Highly Efficient Chiral Recognition and Amplification

Wang,

Hao,

Xing

2023

Chem. Mater.

View full text Add to dashboard Cite

show abstract

“…Because stereospecific reactions utilizing the chirally oriented crystals as a substrate have been reported, [31][32][33][34][35][36][37] enantioenriched chiral compounds could be obtained based on the crystal chirality of achiral compounds.…”

Section: Introductionmentioning

confidence: 99%

Achiral 2‐pyridone and 4‐aminopyridine act as chiral inducers of asymmetric autocatalysis with amplification of enantiomeric excess via the formation of chiral crystals

Matsumoto,

Tateishi,

Nakajima

et al. 2023

Chirality

Self Cite

View full text Add to dashboard Cite

Enantiomorphous crystals of achiral 2‐pyridone and 4‐aminopyridine served as sources of chirality, to induce the asymmetric autocatalysis of 5‐pyrimidyl alkanol during the asymmetric addition of diisopropylzinc to the corresponding pyrimidine‐5‐carbaldehyde, that is, the Soai reaction. Following a significant amplification of enantiomeric excess through asymmetric autocatalysis, highly enantioenriched 5‐pyrimidyl alkanol could be synthesized with their corresponding absolute configurations to those of chiral crystals of 2‐pyridone and 4‐aminopyridine.

show abstract

Enantiomer Recognition by the Difference in Adsorption Rates on the Surfaces of Chiral Crystals

Belonogov,

Ermolaeva,

Zinoviev

et al. 2024

Chirality

View full text Add to dashboard Cite

The chirality of biopolymers remains one of the mysteries of Life. For such objects, the phenomenon of supramolecular chirality (SMC) is vital. Enantiomers can be recognized by the adsorption on surfaces with SMC. However, the mechanisms of such chiral recognition are still unknown. In this work, the adsorption kinetics of menthol test enantiomers on the surfaces of γ‐glycine and NiSO4•6H2O chiral crystals was studied. It was found that the difference in adsorption was observed in nonequilibrium state more often than in equilibrium. If the enantioselectivity in equilibrium state was observed, the enantioselectivity coefficient α at nonequilibrium conditions was higher. The maximum α in nonequilibrium state was 2.44 for γ‐glycine crystals and 2.12 for NiSO4•6H2O crystals. Even if no differences in adsorption were observed under adsorption–desorption equilibrium conditions, a significant enantioselectivity at nonequilibrium conditions was found. This has proved the possibility of chiral recognition on surfaces with SMC by the differences in adsorption rates. Such novel chiral recognition mechanism can provide enhanced enantioselectivity in adsorption, catalysis, chromatographic separation, and chemical sensing.

show abstract

Chirally and chemically reversible Strecker reaction

Abstract: Regarding a credible abiotic synthesis mechanism of α-amino acids, solid-state asymmetric Strecker/retro-Strecker reactions have been demonstrated. Arising from the enantiomorph crystals of achiral imines, asymmetric cyanide addition proceeded to produce...

Cited by 7 publications

References 60 publications

Phosphorescent Thermal Chiroptical Switch Built through Highly Efficient Chiral Recognition and Amplification

Phosphorescent Thermal Chiroptical Switch Built through Highly Efficient Chiral Recognition and Amplification

Achiral 2‐pyridone and 4‐aminopyridine act as chiral inducers of asymmetric autocatalysis with amplification of enantiomeric excess via the formation of chiral crystals

Enantiomer Recognition by the Difference in Adsorption Rates on the Surfaces of Chiral Crystals

Contact Info

Product

Resources

About