Synlett 2019; 30(08): 932-938
DOI: 10.1055/s-0037-1611780
letter
© Georg Thieme Verlag Stuttgart · New York

Acetic Acid-Promoted Rhodium(III)-Catalyzed Hydroarylation of Terminal Alkynes

Chang-Lin Duan
a  Department of Chemistry, Shanghai Normal University, 100 Guilin Road, Shanghai 200234, P. R. of China   Email: shipingy@shnu.edu.cn
b  CAS Key Laboratory of Synthetic Chemistry of Natural Substances,Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China   Email: tianping@sioc.ac.cn   Email: lingq@sioc.ac.cn
,
Xing-Yu Liu
b  CAS Key Laboratory of Synthetic Chemistry of Natural Substances,Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China   Email: tianping@sioc.ac.cn   Email: lingq@sioc.ac.cn
d  School of Physical Science and Technology, ShanghaiTech University, 100 Haike Road, Shanghai 201210, P. R. of China
,
Yun-Xuan Tan
b  CAS Key Laboratory of Synthetic Chemistry of Natural Substances,Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China   Email: tianping@sioc.ac.cn   Email: lingq@sioc.ac.cn
,
Rui Ding
c  Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, 1200 Cailun Road, Shanghai 201203, P. R. of China   Email: tianping@shutcm.edu.cn
,
Shiping Yang*
a  Department of Chemistry, Shanghai Normal University, 100 Guilin Road, Shanghai 200234, P. R. of China   Email: shipingy@shnu.edu.cn
,
b  CAS Key Laboratory of Synthetic Chemistry of Natural Substances,Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China   Email: tianping@sioc.ac.cn   Email: lingq@sioc.ac.cn
c  Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, 1200 Cailun Road, Shanghai 201203, P. R. of China   Email: tianping@shutcm.edu.cn
,
Guo-Qiang Lin*
b  CAS Key Laboratory of Synthetic Chemistry of Natural Substances,Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China   Email: tianping@sioc.ac.cn   Email: lingq@sioc.ac.cn
c  Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine, 1200 Cailun Road, Shanghai 201203, P. R. of China   Email: tianping@shutcm.edu.cn
› Author Affiliations
Financial support was generously provided by the NSFC (Nos. 21572251, 21572253, and 21871184), the SMEC (No. 2019-01-07-00-10-E00072), the STCSM (No. 18401933500), the 973 Program (No. 2015CB856600), and the CAS (Nos. XDB 20020100 and QYZDY-SSW-SLH026).
Further Information

Publication History

Received: 18 February 2019

Accepted after revision: 13 March 2019

Publication Date:
26 March 2019 (online)


Both authors contributed equally to this work

Abstract

Rhodium(III)-catalyzed hydroarylation of terminal alkynes has not previously been achieved because of the inevitable oligomerization and other side reactions. Here, we report a novel Cp*Rh(III)-catalyzed hydroarylation of terminal alkynes in acetic acid as solvent to facilitate the C–H bond activation and subsequent transformations. This reaction proceeds under mild conditions, providing an effective approach to the synthesis of alkenylated heterocycles in high to excellent yields (31–99%) with a broad substrate scope (37 examples) and good functional-group compatibility. In this transformation, the loading of the alkyne can be reduced to 1.2 equivalents, which indicates the significant role of HOAc in lowering the reaction temperature and suppressing the oligomerization of the terminal alkyne. Preliminary mechanistic studies are also presented.

Supporting Information

 
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  • 11 2-{2-[(E)-2-Phenylvinyl]phenyl}pyridine (3aa); Typical ProcedureA dried Schlenk tube equipped with a magnetic stirrer bar was charged sequentially with [Cp*RhCl2]2 (3.1 mg, 0.005 mmol, 2.5 mol%), AgSbF6 (10.3 mg, 0.03 mmol, 15 mol%), substrate 1a (0.2 mmol), HOAc (1 mL), and ethynylbenzene (2a; 0.24 mmol) under argon. The mixture was then stirred at rt for 12 h. When the reaction as complete, the mixture was diluted with EtOAc (10 mL), filtered through a short pad of silica gel that was washed with EtOAc (30 mL). The filtrate was adsorbed on silica gel and concentrated by rotary evaporation. The crude product was purified by flash chromatography [silica gel (300–400 mesh); PE/EA (9:1)] to give a yellow oil; yield: 48.3 mg (94%).1H NMR (400 MHz, CDCl3): δ = 8.76 (d, J = 4.4 Hz, 1 H), 7.80–7.71 (m, 2 H), 7.56 (d, J = 6.5 Hz, 1 H), 7.48–7.36 (m, 5 H), 7.34–7.19 (m, 5 H), 7.06 (d, J = 16.2 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 158.8, 149.4, 139.4, 137.6, 136.2, 135.7, 130.3, 130.2, 128.7, 128.6, 127.7, 127.6, 127.5, 126.6, 126.3, 125.1, 121.9.