Key Laboratory of Flexible Electronics & Institute of Advanced Materials, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, 30 South Puzhu Road, Nanjing, 211816, China.
College of Chemistry, Zhengzhou University, 100 Science Avenue, Zhengzhou, Henan Province, 450001, China.
Nat Commun. 2020 Feb 19;11(1):946. doi: 10.1038/s41467-020-14799-8.
Amides are among the most fundamental functional groups and essential structural units, widely used in chemistry, biochemistry and material science. Amide synthesis and transformations is a topic of continuous interest in organic chemistry. However, direct catalytic asymmetric activation of amide C-N bonds still remains a long-standing challenge due to high stability of amide linkages. Herein, we describe an organocatalytic asymmetric amide C-N bonds cleavage of N-sulfonyl biaryl lactams under mild conditions, developing a general and practical method for atroposelective construction of axially chiral biaryl amino acids. A structurally diverse set of axially chiral biaryl amino acids are obtained in high yields with excellent enantioselectivities. Moreover, a variety of axially chiral unsymmetrical biaryl organocatalysts are efficiently constructed from the resulting axially chiral biaryl amino acids by our present strategy, and show competitive outcomes in asymmetric reactions.
酰胺是最基本的功能基团和重要的结构单元之一，广泛应用于化学、生物化学和材料科学。酰胺的合成和转化是有机化学中一个持续关注的课题。然而，由于酰胺键的高稳定性，直接催化不对称活化酰胺 C-N 键仍然是一个长期存在的挑战。在此，我们描述了在温和条件下通过有机催化不对称酰胺 C-N 键断裂来实现 N-磺酰基联芳基内酰胺的去对称化，发展了一种通用且实用的方法，用于轴手性联芳基氨基酸的构建。通过该方法可以以高收率和优异的对映选择性得到结构多样的轴手性联芳基氨基酸。此外，通过我们目前的策略，可以从得到的轴手性联芳基氨基酸高效构建各种轴手性非对称联芳基有机催化剂，并在不对称反应中表现出有竞争力的结果。
