Self-Replication of Chiral α-Amino Acids in Strecker-Type Synthesis via Asymmetric Induction and Amplification of Their Own Chiral Intermediate α-Aminonitriles
Self-Replication of Chiral α-Amino Acids in Strecker-Type Synthesis via Asymmetric Induction and Amplification of Their Own Chiral Intermediate α-Aminonitriles
复制标题
DOI：
10.1246/bcsj.20190116
复制
发表时间：
2019-10-01
影响因子：
4
通讯作者：
Kawasaki, Tsuneomi
中科院分区：
文献类型：
--
作者：
Aiba, Shohei;Tanaka, Yudai;Kawasaki, Tsuneomi
自我复制是生命的基本特征之一，因此，生物相关的手性对映体富集化合物能够促进自身生产的化学反应是广泛科学领域中一个有吸引力的挑战。在这里，我们发现了不对称Strecker型合成，其中手性L-和D-α-氨基酸对映选择性地分别诱导其自身的固态手性中间体L-和D-α-氨基腈的形成和扩增。因此，氨基腈水解后，可以重复生产与原始化合物具有相同结构和相同绝对构型的对映体富集氨基酸，并改善对映体过量。继我们首次报道α-(对甲苯基)甘氨酸的复制之后，我们发现α-(1-萘基)甘氨酸和α-(邻甲苯基)甘氨酸的对映体也可以通过相应氨基腈的扩增在Strecker型合成中复制增殖。从绝对不对称Strecker型氨基酸合成的角度，讨论α-氨基腈的自发形成、扩增和增殖，即对映选择性反应结晶。
Self-replication is one of the essential characteristics of life, therefore, chemical reaction, in which biologically related chiral enantioenriched compounds can promote their own production, is an attractive challenge in broad scientific fields. Here, we found asymmetric Strecker-type synthesis, in which chiral L- and D-alpha-amino acids enantioselectively induced the formation and amplification of their own chiral intermediates L- and D-alpha-aminonitriles in solid state, respectively. Thus, after the hydrolysis of aminonitriles, enantioenriched amino acids with the same structure and the same absolute configuration as that of the original compounds could be replicatively produced with improvement of enantiomeric excess. Following our first report on the replication of alpha-(p-tolyl)glycine, here we found that the enantiomer of alpha-(1-naphthyl)glycine and alpha-(o-tolyl)glycine can also replicatively multiply in the Strecker-type synthesis via the amplification of the corresponding aminonitriles. From the viewpoint of the absolute asymmetric Strecker-type amino acid synthesis, spontaneous formation, amplification and multiplication, i.e., enantioselective reactive crystallization of alpha-aminonitriles will be discussed.