Abstract
We developed a non-toxic cyanation reaction of various aryl halides and triflates in acetonitrile using a catalyst system of [Ni(MeCN)6](BF4)2, 1,10-phenanthroline, and 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine (Si-Me4-DHP). Si-Me4-DHP was found to function as a reductant for generating nickel(0) species and a silylation reagent to achieve the catalytic cyanation via C-CN bond cleavage.
Highlights
All publication charges for this article have been paid for by the Royal Society of Chemistry
We developed a non-toxic cyanation reaction of various aryl halides and triflates in acetonitrile using a catalyst system of [Ni(MeCN)6](BF4)2, 1,10-phenanthroline, and 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl1,4-dihydropyrazine (Si–Me4-DHP)
Si–Me4-DHP was found to function as a reductant for generating nickel(0) species and a silylation reagent to achieve the catalytic cyanation via C–CN bond cleavage
Summary
All publication charges for this article have been paid for by the Royal Society of Chemistry. 83 kcal molÀ1).[10] pivotal studies using acetonitrile as a cyano source were recently achieved at high temperature (120–160 C): Cheng et al used phosphine complexes of palladium and nickel for the catalytic cyanation of ortho-mono and ortho-disubstituted aryl halides with acetonitrile in the presence of zinc powder at elevated temperature (160 C) (Fig. 1a),9d and Shen et al applied a catalyst system of copper(II) nitrate with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) for the cyanation of aryl iodides in acetonitrile at high temperature (150 C) (Fig. 1b).9e,f Quite recently, Morandi et al demonstrated that a combination of bis(acetylacetonato) nickel(II) with Xantphos became a catalyst for the cyanation of aryl chlorides and aryl tri ates with n-butyronitrile as a cyano In this context, we have continuously focused our efforts on nding a catalyst system active for such cyanation using acetonitrile under milder reaction conditions. 54% yield (entries 9 and 10), the latter of which was consistent with the observation that an isolated dicationic tris(1,10-
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