Highly atroposelective synthesis of nonbiaryl naphthalene-1,2-diamine N-C atropisomers through direct enantioselective C-H amination

• Published in: Nature communications Vol. 10; no. 1; pp. 3063 - 9
• Main Authors: Bai, He-Yuan, Tan, Fu-Xin, Liu, Tuan-Qing, Zhu, Guo-Dong, Tian, Jin-Miao, Ding, Tong-Mei, Chen, Zhi-Min, Zhang, Shu-Yu
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 11.07.2019; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/58; 639/638/403/933; 639/638/77/883; 639/638/77/889; Amination; Aromatic compounds; Chemical bonds; Chirality; Diamines; Enantiomers; Humanities and Social Sciences; Hydrogen bonds; multidisciplinary; Naphthalene; Natural products; Science; Science (multidisciplinary); Substrates
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-019-10858-x

Nonbiaryl N-C atropisomer is an important structural scaffold, which is present in natural products, medicines and chiral ligands. However the direct enantioselective C-H amination to access optically pure N-C atropisomer is still difficult and rare. Here we report a π-π interaction and dual H-bond concerted control strategy to develop the chiral phosphoric acids (CPAs) catalyzed direct intermolecular enantioselective C-H amination of N-aryl-2-naphthylamines with azodicarboxylates as amino sources for the construction of atroposelective naphthalene-1,2-diamines. This type of N-C atropisomers is stabilized by intramolecular hydrogen bond and the method features a broad range of substrates, high yields and ee values, providing a strategy to chirality transfer via the modification of N-C atropisomers. Atropisomers with a chiral C-N axis are useful for natural products synthesis and as ligands in asymmetric catalysis. Here, the authors reportt a π-π interaction and dual H-bond concerted control strategy in enantioselective C-H amination affording configurationally stable N-C atropisomers.