Stereospecific Oxycyanation of Alkenes with Sulfonyl Cyanide
Intermolecular oxycyanation of alkenes using p-toluenesulfonyl cyanide (TsCN) in the presence of tris(pentafluorophenyl)borane (B(C6F5)3) as a catalyst was shown to be feasible. The developed method offers a simple, scalable, and straightforward approach to access synthetically useful β-hydroxy nitrile derivatives.
Oxycyanation of alkenes would allow the direct construction of useful β-hydroxy nitrile scaffolds. However, only limited examples of such reactions have been reported, and some problems including limited substrate scope and the lack of diastereocontrol in the case of the oxycyanation of internal alkenes have arisen. We herein report on the intermolecular oxycyanation of alkenes using p-toluenesulfonyl cyanide (TsCN) in the presence of tris(pentafluorophenyl)borane (B(C6F5)3) as a catalyst, affording products that contain a sulfinyloxy group and a cyano group at the vicinal position. The reaction features a stereospecific syn-addition. The reaction also shows a broad substrate scope with good functional group tolerance. Mechanistic investigations by experimental studies and density functional theory (DFT) calculations revealed that the reaction proceeds via an unprecedented stereospecific mechanism through the electrophilic cyanation of alkenes, in which B(C6F5)3 efficiently activates TsCN through the coordination of the cyano group to the boron center.Zum Volltext
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