Eliminative Wacker Oxidation: An Efficient Synthesis of α-Alkyl Vinyl Methyl Ketones

Abstract

A new facet of Wacker oxidation of substituted 4-pentenals has been reported wherein concomitant elimination takes place during Wacker oxidation to yield α-alkyl vinyl methyl ketones.

Key words

Wacker oxidation - allyl vinyl ether - 4-pentenal - α-alkyl vinyl methyl ketone - elimination

References

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  Spectral data of the chloromethyl ether: ¹H NMR (90 MHz, CDCl₃): δ = 4.17 (d, J = 5.65 Hz, 2 H, CH ₂OBn), 4.31 (d, J = 5.65 Hz, 2 H, CH ₂OCH₂Cl), 4.59 (s, 2 H, OCH ₂Ph), 5.51 (s, 2 H, OCH₂Cl), 5.63-6.17 (m, 2 H, CH=CH), 7.43 (s, 5 H, C₆H₅). ¹³C NMR (22.5 MHz, CDCl₃): δ = 70.5, 73.1, 75.9, 86.1, 127.1, 128.9, 129.5, 130.1, 137.1. Anal. Calcd for C₁₂H₁₅ClO₂: C, 63.57; H, 6.67. Found: C, 63.86; H, 6.85.

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  Spectral data of the phosphonium salt I: ¹H NMR (300 MHz, CDCl₃): δ = 4.09 (d, J = 6.3 Hz, 2 H, CH ₂OBn), 4.47 (s, 2 H, OCH ₂Ph), 4.53 (d, J = 6.3 Hz, 2 H, CH ₂OCH₂PPh₃), 5.56-5.65 (m, 1 H, CH=CH), 5.76-5.84 (m, 1 H, CH=CH), 5.97 (d, J = 4.2 Hz, 2 H, CH ₂PPh₃), 7.28-7.84 (m, 20 H, ArH). ¹³C NMR (22.5 MHz, CDCl₃): δ = 61.1, 64.1, 64.8, 68.4, 69.1, 71.1, 113.4, 117.2, 125.5, 126.5, 127.1, 128.9, 129.4, 130.2, 132.6, 133.1, 134.1, 137.1. Anal. Calcd for C₃₀H₃₀ClO₂P: C,73.68; H, 6.18. Found: C, 73.47; H, 6.44.

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