Nickel-Catalyzed Favorskii-Type Rearrangement of Cyclobutanone Oxime Esters to Cyclopropanecarbonitriles

Abstract

A nickel-catalyzed base-promoted rearrangement of cyclo­butanone oxime esters to cyclopropanecarbonitriles was developed. The ring opening of cyclobutanone oxime esters occurs at the sterically less hindered side. A base-promoted nickelacyclobutane intermediate, formed in situ, is assumed to be involved in the formation of the product.

Key words

nickel catalysis - cyclobutanone oxime esters - cyclopropanecarbonitriles - ring opening - Favorskii rearrangement

Publication History

Received: 14 January 2020

Accepted: 09 March 2020

Article published online:
30 March 2020

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• 14 Cyclopropanecarbonitriles 2; General Procedure In a glove box, a 4 mL screw-capped vial was charged with the appropriate oxime ester 1 (0.2 mmol), NiCl₂(glyme) (4 mg, 0.02 mmol), dtbbpy (5 mg, 0.02 mmol), and DMF (0.2 mL). The mixture was then stirred for 15 min at rt, and a 1.0 M solution of LiHMDS in THF (0.4 mL, 0.4 mmol) was added. The vial was removed from the glove box, and the mixture was stirred at rt for 12 h. The reaction was then quenched with 1 N sat. aq NH₄Cl and diluted with EtOAc. The organic layer was separated, dried (Na₂SO₄), filtered, and concentrated under a vacuum. The product was then obtained by flash chromatography. 1-(4-sec-Butylphenyl)cyclopropanecarbonitrile (2d) Yellow oil; yield: 35.85 mg (90%). ¹H NMR (400 MHz, CDCl₃): δ = 7.19 (d, J = 8.2 Hz, 2 H), 7.12 (d, J = 8.3 Hz, 2 H), 2.45 (d, J = 7.2 Hz, 2 H), 1.84 (dt, J = 13.5, 6.7 Hz, 1 H), 1.72–1.66 (m, 2 H), 1.41–1.34 (m, 2 H), 0.89 (d, J = 6.6 Hz, 6 H). ¹³C NMR (101 MHz, CDCl₃): δ = 141.29, 133.20, 129.59, 125.59, 122.82, 44.87, 30.17, 22.29, 17.93, 13.50. HRMS (EI): m/z [M]⁺ calcd for C₁₄H₁₇N: 199.1356; found: 199.1355. 1-(Phenylselanyl)cyclopropanecarbonitrile (2l) Yellow oil; yield: 39.69 mg (89%). ¹H NMR (400 MHz, CDCl₃): δ = 7.70–7.61 (m, 2 H), 7.38 (dd, J = 5.0, 1.9 Hz, 3 H), 1.74–1.67 (m, 2 H), 1.41–1.35 (m, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 133.74, 129.58, 128.82, 128.27, 122.70, 18.31, 2.62. HRMS (EI): m/z [M]⁺ calcd for C₁₀H₉N⁸⁰Se: 222.9895; found: 222.9894.