Olefin Cross-Metathesis with 3-Nitropropene

Abstract

The synthesis of functionalized allylic nitro compounds via cross-metathesis with a new cross-metathesis partner, 3-nitropropene, is reported. The reaction of various terminal olefins with 3-nitropropene, promoted by 5 mol% of standard commercially available ruthenium pre-catalysts in the presence of triphenyl ­borate, provided the substituted β,γ-nitroolefins in moderate to high yields. These results render the catalytic olefin cross-metathesis as a mild and selective method for the synthesis of allylic nitro compounds.

Key words

ruthenium - catalysis - olefin metathesis - Lewis acids - nitroolefins

References and Notes

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19

General Setup for CM Reactions with 3-Nitropropene: Reactions were carried out under argon in pre-dried glassware using Schlenk techniques. Solvents were dried by distillation over CaH₂ under argon and stored under an argon atmosphere. Olefin metathesis pre-catalysts were obtained from Sigma-Aldrich (1b, 1c) and Apeiron Catalysts (1d, www.apeiron-catalysts.com). All other commercially available chemicals were used as received. Comparative CM experiments (refer to Tables  [¹] and  [²] ) were conducted with an internal standard (tetradecane) and analyzed by GC. The responses of the FID detector were calibrated using 3a/tetradecane and 4a/tetradecane standard solutions. Each CM experiment was repeated at least twice.

20

Representative Procedure of CM Reaction. To a solution of alkene 3b (1.23 mmol, 240.8 mg) and 3-nitropropene (2.63 mmol, 228.6 mg) in CH₂Cl₂ (5 mL), triphenyl borate (0.30 mmol, 87.6 mg, 25 mol%) was added. Next, ruthenium pre-catalyst 1d was added in one portion (0.06 mmol, 40.8 mg, 5 mol%) and the resulting mixture was refluxed for 5 h under an argon atmosphere. The solvent was removed under reduced pressure. The crude product was purified by flash chromatography (cyclohexane-EtOAc = 20:1) to yield the analytically pure product 4b as an yellow oil (0.89 mmol, 227.4 mg, 73%) as a mixture of E/Z isomers (in 5.2:1 ratio). Analytical data: ^¹H NMR (400 MHz, CDCl₃; E-isomer): δ = 5.92 (dtt, J = 15.3, 6.8, 1.0 Hz, 1 H), 5.74 (dtt, J = 15.3, 7.2, 1.4 Hz, 1 H), 4.87 (dd, J = 7.2, 0.8 Hz, 2 H), 2.09-2.14 (m, 2 H), 1.26 (m, 20 H), 0.88 (t, J = 6.8 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃; E-isomer): δ = 141.9 (CH), 118.4 (CH), 77.7 (CH₂), 32.3 (CH₂), 31.9 (CH₂), 29.6 (CH₂), 29.64 (CH₂), 29.61 (CH₂), 29.5 (CH₂), 29.4 (CH₂), 29.3 (CH₂), 29.13 (CH₂), 29.07 (CH₂), 28.5 (CH₂), 22.7 (CH₂), 14.1 (Me).
MS (ESI): m/z = 278 [M + Na]⁺. IR (neat): 2925, 2854, 1557, 1467, 1375, 970 cm^-¹. Anal. Calcd for C₁₅H₂₉NO₂: C, 70.54; H, 11.45; N, 5.48. Found: C, 70.41; H, 11.57; N, 5.42.