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Synlett 2011(7): 887-890  
DOI: 10.1055/s-0030-1259719
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Efficient Approach to Alkenyl Nitriles from Allyl Esters

Wang Zhoua,b, Jiaojiao Xub, Liangren Zhangb, Ning Jiao*b,c
a College of Chemical Engineering, Xiangtan University, Hunan 411105, P. R. of China
b State Key Laboratory of Natural and Biomimetic Drugs, Peking University, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191, P. R. of China
Fax: +86(10)82805297; e-Mail: jiaoning@bjmu.edu.cn;
c State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
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Publication History

Received 2 December 2010
Publication Date:
10 March 2011 (online)

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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

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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.