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

• 成果类型: Article
• 署名作者: Li, Panpan; Zheng, En; Li, Guanlin; Luo, Yicong; Huo, Xiaohong; Ma, Shengming; Zhang, Wanbin
• 署名单位: Shanghai Jiao Tong University; Chinese Academy of Sciences; University of Chinese Academy of Sciences, CAS; Shanghai Institute of Organic Chemistry, CAS; Fudan University
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-12635
• DOI: 10.1126/science.ado4936
• 发表日期: 2024-08-30
• 页码: 972-979
• 关键词: organometallic conformational equilibria; synthetic applications; asymmetric-synthesis; allylic alkylations; allenes; alkenes; isomerization; olefination; bonds

摘要

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 alpha-amino acids are highly sought after in organic and medicinal chemistry. In this study, we report a ligand-controlled stereodivergent synthesis of non-natural alpha-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.