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Copper(I) halides inhibit olefin isomerized by-products from phosphine-based Grubbs’ metathesis catalysts in polar protic solvents

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Abstract

Copper(I) halides are employed as ‘phosphine sponges’ to sequester phosphor-ylides when using phosphine-based Grubb’s metathesis catalysis in polar protic solvents and under heat. These cuprous halides are hypothesized to significantly slow the formation of the ruthenium hydride olefin isomerization catalyst. We demonstrate their use in both cross metathesis and ring-closing metathesis.

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Notes

  1. General experimental procedure: To a clean flask was added Grubbs' first-generation catalyst (17 mg, 21 μmol, 1 mol %) dissolved in 1 mL dichloromethane under inert atmosphere. To the flask was then added 5 mL of 1:1 MeOH:Ethylene glycol followed by NaI (3.2 mg, 21 μmol, 1 mol %). To the flask was added 1-propenyldiphenylphosphine oxide (509 mg, 2.1 mmol), and the reaction mixture was maintained at 50 °C using a temperature controlled oil-bath for 22 h. For analysis, an aliquot was drawn, dissolved in CDCl3 (containing 1 % TMS internal standard), and sample analyzed by 1H NMR. The ratio of peaks occurring at 6.69 ppm (isomerization product) and 5.70 ppm (metathesis product) was taken to calculate the ratio of the isomerization versus metathesis reactions—keeping in mind that the ratio of the peak at 5.70 ppm represents twice as many protons. 1H NMR (CDCl3) data: 1.20 (m, 3H, isomerized CH3), 2.62 (m 4H, metathesis CH2), 5.65 (m, 2H, metathesis CH), 6.28 (m, 1H, isomerized CH), 6.70 (m, 1H, isomerized CH), 7.49 (m, 12H, Ph), 7.70 (m, 8H, Ph). Isomerized: metathesis ratio = 1:1. All other reactions were performed following this procedure.

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Acknowledgments

We acknowledge support from University of Massachusetts Boston through start-up funds to MMT. We are grateful to Dr. Rafael E. Luna, of Luna Scientific Storytelling.

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Correspondence to Martin M. Thuo.

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Schulz, M.D., Atkinson, M.B.J., Elsey, R.J. et al. Copper(I) halides inhibit olefin isomerized by-products from phosphine-based Grubbs’ metathesis catalysts in polar protic solvents. Transition Met Chem 39, 763–767 (2014). https://doi.org/10.1007/s11243-014-9858-1

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