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Synlett 2020; 31(12): 1211-1215
DOI: 10.1055/s-0040-1708015
DOI: 10.1055/s-0040-1708015
letter
Formation of Imidazolones by Ring Closure of α-Isocyanoamides: Exploring New Reactivities
This work has been partially supported by INSA Rouen, Rouen University, CNRS, EFRD, European INTERREG IV A France (Channel) and Labex SynOrg (ANR-11-LABX-0029). S.F. is grateful to the Region Normandie for a grant.Further Information
Publication History
Received: 10 March 2020
Accepted after revision: 27 March 2020
Publication Date:
16 April 2020 (online)
Abstract
Base-mediated ring closure of α,α-disubstituted α-isocyanoamides with further electrophilic trapping has previously been explored, but with limited applications. In this work, we wished to unravel the reactivities of these compounds and, in particular, to allow palladium-catalyzed coupling at the C2 position.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1708015.
- Supporting Information
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References and Notes
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- 16 3-Benzyl-2-(4-methoxyphenyl)-1,3-diazaspiro[4.4]non-1-en-4-one (3c); One-Pot Procedure A 2.5 M solution of BuLi in hexanes (0.42 mL, 1.056 mmol, 1.2 equiv) was added dropwise to a solution of isocyanoamide 1 (200 mg, 0.88 mmol) in dry THF (35 mL) at –78 °C, and the mixture was stirred for 1 h at –78 °C. NBS (188 mg, 1.056 mmol, 1.2 equiv) was introduced into the solution, and the mixture was allowed to warm to r.t. The mixture was then concentrated to ~1 mL and introduced into a sealed tube containing a magnetic stirrer bar. (4-Methoxyphenyl)boronic acid (1.32 mmol, 1.5 equiv), K2CO3 (4.24 mmol, 4 equiv), and PdCl2(dppf) (0.1 equiv, 0.088 mmol) were added, followed by 1,4-dioxane (4 mL) and H2O (2 mL). The mixture was degassed and placed under N2, and the tube was sealed and heated at 80 °C for 18 h. The mixture was then filtered through a Celite pad, washing with CH2Cl2. The solvents were removed under reduced pressure, and the crude product was purified by gradient column chromatography [silica gel, PE to PE–EtOAc (80:20)] to give a pale yellow oil (199 mg, 68%). 1H NMR (300 MHz, DMSO-d 6): δ = 7.47 (d, J = 8.79 Hz, 2 H, HArom), 7.31–7.21 (m, 3 H, HArom), 7.00–6.97 (m, 2 H, HArom), 6.95 (d, J = 8.79 Hz, 2 H, HArom), 4.76 (s, 2 H, HBn), 3.77 (s, 3 H, HMeO), 1.95–1.80 (m, 8 H, HCy). 13C NMR (75 MHz, DMSO-d 6): δ = 186.3, 161.0, 159.5, 137.0, 129.6, 128.7, 127.2, 126.0, 121.9, 113.9, 76.3, 55.3, 44.1, 37.2, 25.5.
For examples of transformations of oxazolones into imidazolones by condensation reactions, see: