A reaction mode of carbene-catalysed aryl aldehyde activation and induced phenol OH functionalization

• Main Authors: Chen, Xingkuan, Wang, Hongling, Doitomi, Kazuki, Ooi, Chong Yih, Zheng, Pengcheng, Liu, Wangsheng, Guo, Hao, Yang, Song, Song, Bao-An, Hirao, Hajime, Chi, Yonggui Robin
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2018
• Subjects: Carbene; Aldehyde
• Online Access: https://hdl.handle.net/10356/87071; http://hdl.handle.net/10220/44271
• Institution: Nanyang Technological University

The research in the field of asymmetric carbene organic catalysis has primarily focused on the activation of carbon atoms in non-aromatic scaffolds. Here we report a reaction mode of carbene catalysis that allows for aromatic aldehyde activation and remote oxygen atom functionalization. The addition of a carbene catalyst to the aldehyde moiety of 2-hydroxyl aryl aldehyde eventually enables dearomatization and remote OH activation. The catalytic process generates a type of carbene-derived intermediate with an oxygen atom as the reactive centre. Inexpensive achiral urea co-catalyst works cooperatively with the carbene catalyst, leading to consistent enhancement of the reaction enantioselectivity. Given the wide presence of aromatic moieties and heteroatoms in natural products and synthetic functional molecules, we expect our reaction mode to significantly expand the power of carbene catalysis in asymmetric chemical synthesis.