Trifluoroacetic acid → Hepta-2,6-dienoic Acid

Participants

Reaction Steps

To a solution of oxalyl chloride (3.36 mL, 39.2 mmol) in CH2Cl2 (100 mL) at −78° C. was added DMSO (5.56 mL, 78.3 mmol). After stirring for 5 min, 4-penten-1-ol (2.00 mL, 19.6 mmol) was added, and after another 15 min Et3N (13.6 mL, 97.9 mmol) was added. The reaction mixture was warmed to rt and then treated with 0.1M HCl. The organic layer was separated, washed with saturated aqueous NaCl solution, dried (MgSO4), and treated with Ph3PCHCO2t-Bu (7.38 g, 19.6 mmol) at rt. The reaction mixture was stirred for 5 h and then treated with saturated aqueous NH4Cl solution and diluted with CH2Cl2. The organic layer was separated and the aqueous layer was extracted with CH2Cl2 (3×). The combined organic layers were dried (MgSO4) and concentrated under reduced pressure. The crude product was filtered through a silica plug (CH2Cl2/pentane 1:1) to give t-butyl (E)-2,6-heptadienoate. To a solution of this ester in CH2Cl2 (40 mL) was added TFA (5 mL) at rt. After stirring for 12 h, the reaction mixture was concentrated under reduced pressure. Purification of the crude product by FC (hexane/EtOAc 15:1→5:1) afforded 2,6-heptadienoic acid 6 (1.67 g, 68%) as a colorless oil. 1H-NMR (400 MHz, CDCl3) δ 7.12-7.05 (m, 1H), 5.88-5.76 (m, 2H), 5.08-5.02 (m, 2H), 2.37-2.32 (m, 2H), 2.26-2.21 (m, 2H).

Provenance & Evidence