上海交通大学张万斌研究团队报道了通过对映体和Z/ e选择性催化获得非天然α-氨基酸的立体发散方法。相关研究成果发表在2024年8月30日出版的《科学》。

烯烃合成中碳-碳双键的Z和E构型的精确控制长期以来一直是合成化学中的一个基本挑战，在同时努力实现对映选择性[（Z，R），（Z，S），（E，R）和（E，S）]时更为明显。此外，对映体纯非天然α-氨基酸在有机和药物化学中备受追捧。

该文中，研究人员报道了一种配体控制的具有三取代烯烃部分的非天然α-季氨基酸的立体发散合成方法，该方法具有高产率和优异的对映选择性和Z/E选择性。其成功是通过钯/铜共催化的三组分组装实现的，该组装由现成的芳基碘化物、二烯烃和醛亚胺酯组成，只需调节钯和铜催化剂的手性配体即可。

附：英文原文

Title: Stereodivergent access to non-natural α-amino acids via enantio- and Z/E-selective catalysis

Author: Panpan Li, En Zheng, Guanlin Li, Yicong Luo, Xiaohong Huo, Shengming Ma, Wanbin Zhang

Issue&Volume: 2024-08-30

Abstract: The precise control of Z and E configurations of the carbon-carbon double bond in alkene synthesis has long been a fundamental challenge in synthetic chemistry, even more pronounced when simultaneously striving to achieve enantioselectivity [(Z,R), (Z,S), (E,R), (E,S)]. Moreover, enantiopure non-natural α-amino acids are highly sought after in organic and medicinal chemistry. In this study, we report a ligand-controlled stereodivergent synthesis of non-natural α-quaternary amino acids bearing trisubstituted alkene moieties in high yields with excellent enantioselectivity and Z/E selectivities. This success is achieved through a palladium/copper–cocatalyzed three-component assembly of readily available aryl iodides, allenes, and aldimine esters by simply tuning the chiral ligands of the palladium and copper catalysts.

DOI: ado4936

Source: https://www.science.org/doi/10.1126/science.ado4936