A Facile Perfluoroallylation of Olefins

• Published in: Journal of organic chemistry Vol. 63; no. 9; pp. 2887 - 2891
• Main Authors: Nguyen, Ba V, Yang, Zhen-Yu, Burton, Donald J
• Format: Journal Article
• Language: English
• Published: American Chemical Society 01-05-1998
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo9719766

The addition of F-allyl iodide to terminal alkenes is induced by a catalytic amount of copper powder in the absence of solvent at room temperature to 50 °C to give the corresponding 1:1 adducts in good yields. A variety of functional groups such as trimethylsilyl, alkyl, epoxy, ester, hydroxyl, bromo, ether, and phosphonate are tolerated in the addition reaction. This reaction also worked well with internal olefins such as cyclohexene, cyclopentene, and 4-octene. Reaction with dienes gives the corresponding linear adduct and cyclization adduct depending on the chain length of the dienes. With 1,7-octadiene, a bis(perfluoroallyl) product is formed, while a tetrahydrofuran derivative is obtained with diallyl ether. Reduction of the adducts with zinc in the presence of nickel dichloride in moist THF or zinc in moist DMF affords the perfluoroallyl derivatives. The adduct reacts with zinc in DMF to form a zinc reagent which couples with organic electrophiles in the presence of CuBr.