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

Chang-Lin Duan; Xing-Yu Liu; Yun-Xuan Tan; Rui Ding; Shiping Yang; Ping Tian; Guo-Qiang Lin

doi:10.1055/s-0037-1611780

Synlett, Table of Contents

Synlett 2019; 30(08): 932-938
DOI: 10.1055/s-0037-1611780

letter

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

Chang-Lin Duan

^aDepartment of Chemistry, Shanghai Normal University, 100 Guilin Road, Shanghai 200234, P. R. of China Email: shipingy@shnu.edu.cn

^bCAS 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

^bCAS 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

^dSchool of Physical Science and Technology, ShanghaiTech University, 100 Haike Road, Shanghai 201210, P. R. of China

,

Yun-Xuan Tan

^bCAS 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

^cInnovation 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*

^aDepartment of Chemistry, Shanghai Normal University, 100 Guilin Road, Shanghai 200234, P. R. of China Email: shipingy@shnu.edu.cn

,

Ping Tian *

^bCAS 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

^cInnovation 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*

^bCAS 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

^cInnovation 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

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Abstract

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^◊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.

Key words

acetic acid - rhodium catalysis - hydroarylation - alkynes

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References

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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.

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