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

Bin Shuai; Ping Fang; Tian-Sheng Mei

doi:10.1055/s-0039-1690872

Synlett, Table of Contents

Synlett 2021; 32(16): 1637-1641
DOI: 10.1055/s-0039-1690872

cluster

Modern Nickel-Catalyzed Reactions

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

Bin Shuai

,

Ping Fang∗

,

Tian-Sheng Mei∗

State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, P. R. of China

› Author Affiliations

Abstract

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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

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References

References and Notes

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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.

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