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Synlett 2021; 32(16): 1629-1632
DOI: 10.1055/s-0040-1706683
DOI: 10.1055/s-0040-1706683
cluster
Modern Nickel-Catalyzed Reactions
Nickel Hydride Catalyzed Cleavage of Allyl Ethers Induced by Isomerization
Financial support from the German Academic Exchange Service New Delhi, the Deutscher Akademischer Austauschdienst (fellowship for P.K.), and the University of Tübingen is gratefully acknowledged.
Abstract
This report discloses the deallylation of O- and N-allyl functional groups by using a combination of a Ni-H precatalyst and excess Brønsted acid. Key steps are the isomerization of the O- or N-allyl group through Ni-catalyzed double-bond migration followed by Brønsted acid induced O/N–C bond hydrolysis. A variety of functional groups are tolerated in this protocol, highlighting its synthetic value.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1706683.
- Supporting Information
Publication History
Received: 04 November 2020
Accepted: 27 December 2020
Article published online:
22 January 2021
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16
2-Methoxyphenol (2a): Typical Procedure
In a glove box, a flame-dried 15 mL Schlenk tube was charged with [Ni(PMe3)4H]N(SO2CF3)2 (1.6 mg, 2.48 μmol, 1 mol%). The Schlenk tube was removed from the glove box and anhyd THF (1.5 mL, 0.16 M) was added. 1-(Allyloxy)-2-methoxybenzene (1a; 41.1 mg, 0.250 mmol, 1 equiv) was then added under an argon counterflow and the mixture was stirred at RT for 30 min. TsOH·H2O (1 equiv) was added, and the mixture was refluxed for 1 h. The reaction was quenched by addition of EtOAc (2 mL) and H2O (2 mL), and the mixture was transferred to a separatory funnel. The aqueous phase was extracted with EtOAc (3 × 5 mL), and the combined organic phases were dried (MgSO4). Rotary evaporation gave pure 2a, without any chromatographic purification, as a light-brown oil; yield: 26.1 mg (0.21 mmol, 84%). The NMR spectral data matched those reported in the literature.17
Note: The glove box setup for the reaction is not necessary: the catalyst can be stored on the bench under an inert atmosphere.
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