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TCI Practical Example: Cross Metathesis Using UltraNitroCat

We are proud to introduce the cross metathesis using UltraNitroCat as a catalyst.

Used Chemicals

• UltraNitroCat [U0116]
• Acrylonitrile (stabilized with MEHQ) [A0146]
• Ethyl 10-Undecenoate [E0771]
• Anhydrous Toluene
• 1,4-Bis(3-isocyanopropyl)piperazine [B5973]

Procedure

To a solution of ethyl 10-undecenoate (0.400 mL, 1.7 mmol), acrylonitrile (0.210 mL, 3.2 mmol) in anhydrous toluene (5.8 mL) at 70 °C under nitrogen, a solution of UltraNitroCat (3.4 mg, 0.005 mmol, 0.3 mol%) in toluene (0.5 mL) was dropwised over 1 h. The mixture was stirred at 70 °C under nitrogen for 3 hours. 1,4-Bis(3-isocyanopropyl)piperazine (0.5 mol%, 5.0 mg) was added to the reaction mixture to deactivate the catalyst. The solvent was removed under reduced pressure to obtain a light yellow oil (0.37 g).
The crude oil was analyzed by gas chromatography. The reaction conversion rate of 1 and 2 were 69.3% and 6.3%, respectively. The selectivity ratio of 1 and 2 was 92 : 8.

Experimenter's Comments

Toluene was dried over molecular sieves 4A and degassed by purging with nitrogen before use.
Preparation of catalyst stock solution: UltraNitroCat (6.9 mg) was dissolved in dry degassed toluene (1.0 mL).
The reaction mixture was analyzed by GC.

Analytical Data

1: 11-Cyano-10-undecenoic acid ethyl ester

¹H NMR (400 MHz, CDCl₃); δ 6.47 (m, 1H), 5.30 (m, 1H), 4.12 (m, 2H), 2.41 (m, 2H), 2.03 (m, 2H), 1.61 (m, 2H), 1.43 (m, 2H), 1.22 (m, 11H).

2: 10-Eicosenedioic acid diethyl ester

¹H NMR (400 MHz, CDCl₃); δ 6.71 (m, 2H), 5.36 (m, 2H), 4.12 (m, 4H), 2.21 (m, 4H), 1.96 (m, 4H), 1.61 (m, 4H), 1.43 (m, 4H), 1.22 (m, 22H).

Lead Reference

• Cyclic Alkyl Amino Ruthenium Complexes—Efficient Catalysts for Macrocyclization and Acrylonitrile Cross Metathesis
  • R. Gawin, A. Tracz, M. Chwalba, A. Kozakiewicz, B. Trzaskwski, K. Skowerski, ACS Catal. 2017, 8, 5443.