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Related to absolute asymmetric synthesis, a stereospecific reaction at the solid/solid interface arising from crystal chirality of the achiral or racemic substrates has not yet been reported. Here, we demonstrate the asymmetric Strecker-type solid/solid reaction between the chiral crystal of a racemic cyanohydrin (kryptoracemate) and the achiral crystal of an ammonium salt to afford highly enantioenriched α-aminonitrile in combination with amplification of chirality. rac -Cyanohydrin provides its chiral surface as a reactive site and the reaction proceeds with dissociation of cyanohydrin; thus, an asymmetric Strecker-type reaction takes place at the interface of the substrate crystals. Strecker synthesis coupled with cyanohydrin synthesis offers a credible abiotic synthesis mechanism of α-amino acids and α-hydroxy acids. For the first time, stereochemical relationship has been found between the two chiral intermediates, aminonitrile and cyanohydrin, which are in equilibrium in the synthesis mechanism.

Biological homochirality of essential components such as L-amino acids and D-sugars is prerequisite for the emergence, evolution and the maintenance of life. Implication of biological homochirality is described. Considerable interest has been focused on the origin and the process leading to the homochirality. Asymmetric autocatalysis with amplification of enantiomeric excess (ee), i.e., the Soai reaction, is capable to link the low ee induced by the proposed origins of chirality such as circularly polarized light and high ee of the organic compound. Absolute asymmetric synthesis without the intervention of any chiral factor was achieved in the Soai reaction., (© 2022. The Author(s), under exclusive licence to Springer Nature B.V.)

Strecker synthesis has long been considered one of the prebiotic reactions for the synthesis of α-amino acids. However, the correlation between the origin of chirality and highly enantioenriched α-amino acids through this method remains a puzzle. In the reaction, it may be conceivable that the handedness of amino acids has been determined at the formation stage of the chiral intermediate α-aminonitrile, that is, the enantioselective addition of hydrogen cyanide to an imine. Herein, an enantiotopic crystal surface of an achiral imine acted as an origin of chirality for the enantioselective formation of α-aminonitriles by the addition of HCN. In conjunction with the amplification of the enantiomeric excess and multiplication of enantioenriched aminonitrile, a large amount of near enantiopure α-amino acids, with the l- and d-handedness corresponding to the molecular orientation of the imine, is reported., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Replication of chiral l- and d-α-(p-tolyl)glycine has been achieved in combination with the asymmetric induction, amplification and multiplication of their own chiral intermediates, l- and d-aminonitriles, in the solid-phase via the Strecker reaction between three achiral components, which is a plausible prebiotic mechanism for amino acid synthesis.

Without the addition of any chiral substances, the spontaneous formation of an enantioenriched α-amino nitrile (up to 96% ee), which is a chiral precursor for Strecker amino acid synthesis, has been achieved in combination with conglomerate formation. The frequency of the formation of enantiomorphs exhibits an approximate stochastic distribution, i.e., L-form occurred 21 times and D-form occurred 22 times, which fulfils the conditions necessary for spontaneous absolute asymmetric synthesis.

Achiral meteoritic amino acids, glycine and alpha-methylalanine, with hydrogen isotope (D/H) chirality, acted as the source of chirality in asymmetric autocatalysis with amplification of ee to afford highly enantioenriched 5-pyrimidyl alkanols.

Abstract: 2‐Methylbenzhydrylamine is a chiral variant of achiral benzhydrylamine; however, the chirality formed from the small difference between the phenyl and o‐tolyl groups is not expected to induce sufficient stereoselectivity in conventional homogeneous reactions. Initiated by the spontaneous formation and asymmetric amplification of the enantioenriched N‐benzhydryl‐α‐aminonitrile forming conglomerate, we here report that (S)‐ and (R)‐configured title amine, upon the Strecker reaction with achiral aldehydes and HCN, afford the corresponding α‐aminonitriles with up to >99.5 % diastereomeric excess, in conjunction with an enhancement of chirality in the solid state. l‐Alanine with 98 % ee was synthesized from the (S)‐amine by using the method discussed here. Achiral aromatic and heteroaromatic aldehydes could also be successfully utilized to afford chiral α‐aminonitriles in a highly stereoselective manner. The stereodivergent synthesis of styrylglycine nitriles has also been accomplished by using racemic and enantioenriched 2‐methylbenzhydrylamine. Thus, accompanied with a small rearrangement of the common substrate from achiral toward chiral, the present reactions induce an enhancement of chirality, and expands the concept of stereoselective synthesis to increase the opportunity to access highly enantioenriched compounds such as α‐amino acids. [ABSTRACT FROM AUTHOR]

Strecker synthesis has long been considered one of the prebiotic reactions for the synthesis of α-amino acids. However, the correlation between the origin of chirality and highly enantioenriched α-amino acids through this method remains a puzzle. In the reaction, it may be conceivable that the handedness of amino acids has been determined at the formation stage of the chiral intermediate α-aminonitrile, that is, the enantioselective addition of hydrogen cyanide to an imine. Herein, an enantiotopic crystal surface of an achiral imine acted as an origin of chirality for the enantioselective formation of α-aminonitriles by the addition of HCN. In conjunction with the amplification of the enantiomeric excess and multiplication of enantioenriched aminonitrile, a large amount of near enantiopure α-amino acids, with the l- and d-handedness corresponding to the molecular orientation of the imine, is reported. [ABSTRACT FROM AUTHOR]

The origin of homochirality of organic compounds such as L-amino acids and D-sugars have intrigued many scientists, and several hypotheses regarding its homochirality have been proposed. According to the statistical theory, small fluctuations in the ratio of the two enantiomers are present in a racemic mixture obtained from the reaction of achiral molecules. We report herein the reaction of pyrimidine-5-carbaldehyde and diisopropylzinc in the presence of achiral amine such as N,N'-dimethylpiperazine, N,N'-diethylpiperazine or N-methylmorpholine but in the absence of a chiral substance. The stochastic formation of (S)- and (R)-pyrimidyl alkanols with detectable ee was observed. This study shows that the slight fluctuation of the enantiomeric ratio of pyrimidyl alkanol produced at the initial reaction step can be enhanced significantly in conjunction with asymmetric autocatalysis with amplification of enantiomeric excess. We believe that the stochastic behavior in the formation of pyrimidyl alkanol constitutes one of the conditions necessary for spontaneous absolute asymmetric synthesis. [ABSTRACT FROM AUTHOR]

Without the addition of any chiral substances, the spontaneous formation of an enantioenriched α-amino nitrile (up to 96% ee), which is a chiral precursor for Strecker amino acid synthesis, is achieved in combination with conglomerate formation. [ABSTRACT FROM AUTHOR]

Abstract: Asymmetric autocatalysis of 2-alkynyl-5-pyrimidyl alkanol is employed as a chiral sensor of 20 amino acids. Asymmetric autocatalysis using amino acids as chiral initiators gave pyrimidyl alkanols of the absolute configurations that were correlated with those of the amino acids. The enantiomeric excesses of pyrimidyl alkanol are invariably high even when the enantiomeric excess of amino acids is as low as 0.1%. Thus, by determining the absolute configuration of pyrimidyl alkanol with high enantiomeric excess, one can determine the absolute configuration of amino acids even when their enantiomeric excess is low. [Copyright &y& Elsevier]