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DOI: 10.1055/s-0037-1611780
Acetic Acid-Promoted Rhodium(III)-Catalyzed Hydroarylation of Terminal Alkynes
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).Publication History
Received: 18 February 2019
Accepted after revision: 13 March 2019
Publication Date:
26 March 2019 (online)
![](https://www.thieme-connect.de/media/synlett/201908/lookinside/thumbnails/st-2019-u0095-l_10-1055_s-0037-1611780-1.jpg)
◊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
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611780.
- 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.
For selected recent reviews on transition-metal-catalyzed C–H functionalizations, see:
For selected recent reviews on Cp*Rh(III)-catalyzed C–H functionalizations, see:
For selected recent reviews on C–H functionalizations with alkynes, see:
For selected alkenylation reaction with terminal alkynes catalyzed by other metals, see: