An Efficient Approach to Alkenyl Nitriles from Allyl Esters

Abstract

A novel and efficient approach to alkenyl nitriles from allyl esters has been developed. A tandem Pd-catalyzed substitution and the subsequent oxidative rearrangement are involved in this transformation. The method provides an important supplement for the synthesis of alkenyl nitriles from allyl esters.

Key words

alkenyl nitriles - allyl esters - allyl azides - oxidative rearrangement

References and Notes

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14

Typical Experimental Procedure for the Synthesis of Alkenenitriles 2 from Allyl Esters
An oven-dried Schlenk tube was charge with allyl esters (0.5 mmol), TMSN₃ (0.75 mmol), Pd(PPh₃)₄ (0.025 mmol), and DCE (2 mL) under N₂. The tube was evacuated and refilled with N₂ at -40 ˚C for three times. The mixture was stirred under reflux for 1 h. Then, sulfur (0.1 mmol) and DDQ (0.75 mmol) were added subsequently and carefully under N₂ atmosphere (Caution! N₂ emitted violently). The mixture was stirred under reflux for proper time monitored by TLC, followed by subsequent workup as above. The reaction was cooled down to r.t. After removal of the solvent, the residue was purified by flash chromatography on silica gel (EtOAc-PE, 1:20) to obtain the desired products 2.