Zhu Chendan, Mandrelli Francesca, Zhou Hui, Maji Rajat, List Benjamin
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
J Am Chem Soc. 2021 Mar 10;143(9):3312-3317. doi: 10.1021/jacs.1c00249. Epub 2021 Mar 1.
We report here a scalable, catalytic one-pot approach to enantiopure and unmodified β-amino acids. A newly developed confined imidodiphosphorimidate (IDPi) catalyzes a broadly applicable reaction of diverse bis-silyl ketene acetals with a silylated aminomethyl ether, followed by hydrolytic workup, to give free β-amino acids in high yields, purity, and enantioselectivity. Importantly, both aromatic and aliphatic β-amino acids can be obtained using this method. Mechanistic studies are consistent with the aminomethylation to proceed via silylium-based asymmetric counteranion-directed catalysis (Si-ACDC) and a transition state to explain the enantioselectivity is suggested on the basis of density functional theory calculation.
我们在此报告一种可扩展的、催化一锅法制备对映体纯且未修饰的β-氨基酸的方法。一种新开发的受限亚氨基二磷酸亚胺酯（IDPi）催化各种双硅基乙烯酮缩醛与甲硅烷基化氨基甲基醚发生广泛适用的反应，随后进行水解后处理，以高产率、高纯度和高对映选择性得到游离的β-氨基酸。重要的是，使用该方法可同时获得芳香族和脂肪族β-氨基酸。机理研究表明，氨基甲基化反应通过基于硅鎓的不对称抗衡阴离子导向催化（Si-ACDC）进行，并且基于密度泛函理论计算提出了一个解释对映选择性的过渡态。
