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

被引:55
作者
Chen, Xingkuan [1 ]
Wang, Hongling [2 ]
Doitomi, Kazuki [1 ,3 ]
Ooi, Chong Yih [1 ]
Zheng, Pengcheng [2 ]
Liu, Wangsheng [4 ]
Guo, Hao [4 ]
Yang, Song [2 ]
Song, Bao-An [2 ]
Hirao, Hajime [1 ,3 ]
Chi, Yonggui Robin [1 ,2 ]
机构
[1] Nanyang Technol Univ, Sch Phys & Math Sci, Div Chem & Biol Chem, Singapore 637371, Singapore
[2] Guizhou Univ, Minist Educ, Key Lab Green Pesticide & Agr Bioengn, Lab Breeding Base Green Pesticide & Agr Bioengn, Guiyang 550025, Peoples R China
[3] City Univ Hong Kong, Dept Biol & Chem, Tat Chee Ave, Kowloon Tong 999078, Hong Kong, Peoples R China
[4] Fudan Univ, Dept Chem, 220 Handan Rd, Shanghai 200433, Peoples R China
来源
NATURE COMMUNICATIONS | 2017年 / 8卷
基金
新加坡国家研究基金会; 中国国家自然科学基金;
关键词
N-HETEROCYCLIC CARBENES; DIELS-ALDER REACTIONS; ORGANOCATALYTIC ACTIVATION; COOPERATIVE CATALYSIS; ASYMMETRIC CATALYSIS; GAMMA-BUTYROLACTONES; C(SP(3))-H BONDS; ENALS; QUINODIMETHANES; MULTICATALYSIS;
D O I
10.1038/ncomms15598
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
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.
引用
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页数:8
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