Radical Cyanocarbonylation Using Alkyl Allyl Sulfone Precursors

Abstract

Acyl cyanides have been prepared by the three-component coupling reactions comprised of alkyl allyl sulfones, carbon monoxide, and p-tolylsulfonyl cyanide under tin-free radical reaction conditions.

cyanocarbonylation - acyl radical - tin-free radical reaction - alkyl allyl sulfone - carbon monoxide

References

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10

After removal of heptane from the reaction mixture, IR and ¹³C NMR were taken. IR (polymer): 1711 (C=O), 2343, 2361 (CN) cm^-1. ¹³C NMR (100 MHz, CDCl₃): δ = 114.5 (CN), 178.8 (C=O) cm^-1.

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12

Similarly, quenching with aniline afforded the corresponding amide in 78% yield.

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Typical Procedure:
Heptane (20 mL), 4-phenoxylbutyl allyl sulfone (51 mg, 0.2 mmol), p-tolylsulfonyl cyanide (57 mg, 0.3 mmol), and V-40 (10 mg, 0.04 mmol) were placed in a 50 mL stainless steel autoclave. The autoclave was sealed, purged three times with 10 atm of CO, pressurized with 95 atm of CO, and then heated at 100 °C with stirring for 12 h. After excess CO was discharged at r.t., the reaction mixture was poured into a 100 mL round-bottom flask, quenched with excess MeOH at r.t. for 4 h with stirring. After the solvent and MeOH were removed under reduced pressure, the residue was purified by a silica gel column chromatography using EtOAc and n-hexane (1:20) as eluent to give 5-phenoxypentanoic acid methyl ester (33 mg, 80%) and 5-phenoxypentanenitrile (2 mg, 6%). Caution! All operations should be done carefully inside a fume hood.
5-Phenoxypentanoic Acid Methyl Ester ( 6).
¹H NMR (400 MHz, CDCl₃): δ = 1.79-1.83 (m, 4 H), 2.37-2.40 (m, 2 H), 3.66 (s, 3 H), 3.94-3.97 (m, 2 H), 6.86-6.93 (m, 3 H), 7.26-7.28 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.7, 28.7, 33.7, 51.5, 67.2, 114.6, 120.6, 129.4, 158.9, 173.9. IR (polymer): 693, 756, 1171, 1247, 1498, 1601, 1738, 2951 cm^-1. HRMS: m/z calcd for C₁₂H₁₆O₃ [M⁺] = 208.1099; found: 208.1096.