Huang Yi, Lv Xiaoyan, Tong Hua-Rong, He Wenji, Bai Ziqian, Wang Hao, He Gang, Chen Gong
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China.
Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, China.
Org Lett. 2024 Jan 12;26(1):94-99. doi: 10.1021/acs.orglett.3c03688. Epub 2023 Dec 27.
8-Aminoquinoline (AQ) has proven to be a highly effective bidentate directing group for palladium-catalyzed C-H functionalization reactions. However, enantiocontrol of AQ-directed C(sp)-H functionalization reactions has been challenging. Herein, a new protocol is presented for the Pd-catalyzed enantioselective arylation of unactivated β C(sp)-H bonds of alkyl carboxamides with aryl iodides using a C-iodinated 8-aminoquinolines (IQ) auxiliary in conjugation with a BINOL ligand. Additionally, a C-aryl substituted 8-aminoquinoline auxiliary can facilitate enantioselective alkenylation and alkynylation of benzylic C(sp)-H bonds of 3-arylpropanamides with the corresponding bromide reagents under similar conditions.
8-氨基喹啉（AQ）已被证明是钯催化的C-H官能化反应中一种高效的双齿导向基团。然而，AQ导向的C(sp)-H官能化反应的对映选择性控制一直具有挑战性。在此，提出了一种新的方法，使用与BINOL配体共轭的C-碘化8-氨基喹啉（IQ）辅助剂，实现钯催化的烷基羧酰胺未活化β C(sp)-H键与芳基碘的对映选择性芳基化反应。此外，在类似条件下，C-芳基取代的8-氨基喹啉辅助剂可以促进3-芳基丙酰胺苄基C(sp)-H键与相应溴化物试剂的对映选择性烯基化和炔基化反应。
