Rhodium(III)-Catalyzed ortho C-H Heteroarylation of (Hetero)aromatic Carboxylic Acids: A Rapid and Concise Access to π-Conjugated Poly-heterocycles.
Rh(III)-catalyzed oxidative C-H/C-H cross-coupling between (hetero)aromatic carboxylic acids and various heteroarenes has been accomplished to construct highly functionalized ortho-carboxy-substituted bi(hetero)aryls. The use of a carboxy group as the directing group obviates tedious steps for installation and removal of extra directing groups, and enables a facile one-step synthesis of ortho-carboxy bi(hetero)aryls. The method provides opportunities for rapid assembly of a library of important fluorene and coumarin-type poly-heterocycles through intramolecular electrophilic substitution or oxidative lactonization. As illustrative examples, the strategy developed herein greatly streamlines accesses to a variety of appealing polyheterocycles such as DTPO (5H-dithieno[3,2-b:2',3'-d]pyran-5-one), CPDTO (cyclopentadithiophen-4-one), and indenothiophenes.
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, and State Key Laboratory of Biotherapy, West China Medical School, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (PR China).
Xurong
X
Qin
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, and State Key Laboratory of Biotherapy, West China Medical School, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (PR China).
Xiaoyu
X
Li
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, and State Key Laboratory of Biotherapy, West China Medical School, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (PR China).
Quan
Q
Huang
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, and State Key Laboratory of Biotherapy, West China Medical School, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (PR China).
Hu
H
Liu
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, and State Key Laboratory of Biotherapy, West China Medical School, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (PR China).
Di
D
Wu
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, and State Key Laboratory of Biotherapy, West China Medical School, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (PR China).
Qiang
Q
Guo
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, and State Key Laboratory of Biotherapy, West China Medical School, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (PR China). jingbolan@scu.edu.cn.
Jingbo
J
Lan
College of Materials Science and Engineering, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (PR China).
Ruilin
R
Wang
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, and State Key Laboratory of Biotherapy, West China Medical School, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (PR China). jsyou@scu.edu.cn.
Jingsong
J
You
D002244:Carbon / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D006571:Heterocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
D002264:Carboxylic Acids; D006571:Heterocyclic Compounds; D002244:Carbon; D006859:Hydrogen; D012238:Rhodium
CH activation; conjugation; cross-coupling; heterocycles; rhodium