Practical Synthesis of (Z)-α,β-Unsaturated Nitriles via a One-Pot Sequential Hydroformylation/Knoevenagel Reaction

Abstract

Herein, the synthesis of (Z)-α,β-unsaturated nitriles by a sequential hydroformylation/Knoevenagel reaction has been first developed. A variety of crude α-olefins from Fischer–Tropsch synthesis, internal and special olefins, as well as alkynes could be transformed into value-added alkenyl nitriles (39 examples) up to 90% yield. Remarkably, compared with commonly used tedious multistep reactions, the one-pot protocol features cheap and easily available raw materials, excellent chemo-, regio-, and stereoselectivity, very mild reaction conditions, and easy scale-up production.

Chemoselective α-Alkylation and α-Olefination of Arylacetonitriles with Alcohols via Iron-Catalyzed Borrowing Hydrogen and Dehydrogenative Coupling

“…1, 133.4, 130.8, 130.3, 129.4, 128.9, 128.6, 128.4 Procedure for the Synthesis of 2,3-Diphenylpropanamide 6. 15 To 2,3-diphenylpropanenitrile (62.1 mg, 0.3 mmol) in acetone (2 mL) was added Na 2 CO 3 (159.0 mg, 1.5 mmol) at room temperature. To the suspension was added 35% H 2 O 2 aqueous solution (3.0 mL) at 0 °C and stirred at room temperature.…”

“…Procedure for the Synthesis of 2,3-Diphenylacrylaldehyde 5. 15 To a stirring solution of 2,3-diphenylacrylonitrile 3aa (51.3 mg, 0.25 mmol) in toluene (5.0 mL) was added DIBAL-H (0.35 mmol, 350 μL, 1.4 equiv, 1.0 M in DCM) at −78 °C. The reaction mixture was stirred for 2.5 h at −78 °C and for an additional 2 h at room temperature; then it was slowly quenched with 5% H 2 SO 4 aqueous solution at 0 °C.…”