<i>p</i>-Toluenesulfonyl Cyanide

Griffiths, Gareth

doi:10.1002/047084289x.rt136m.pub2

“…p-Toluenesulfonyl cyanide (TsCN) is a commercially available and widely used cyanating reagent in electrophilic and radical cyanation reactions. [9] In addition, TsCN participates in the sulfonylcyanation of alkenes under radical conditions. [10] Despite its potential as a reagent that can serve as both an oxygen functionality and a cyano group, as of this writing, TsCN has not been applied to the oxycyanation of alkenes.…”

Section: Introductionmentioning

confidence: 99%

Stereospecific Oxycyanation of Alkenes with Sulfonyl Cyanide

Kiyokawa

¹

,

Ishizuka

²

,

Minakata

³

2023

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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(C 6 F 5 ) 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(C 6 F 5 ) 3 efficiently activates TsCN through the coordination of the cyano group to the boron center.

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“…In 2011, the group of Inoue 9 first utilized TsCN as a radical acceptor to realize the photoinduced direct cyanation of the C(sp 3 )-H bond of 1 under the irradiation of a mercury lamp. With benzophenone 3 as a photosensitizer, this reaction provides facile access to nitriles 2 from a wide range of alkanes, cyclic ethers, alcohols, and amines.…”

Section: Photo-induced Cyanation With Tscnmentioning

confidence: 99%

“…2 Among them, tosyl cyanide (TsCN), namely p -toluenesulfonyl cyanide, is a commercially available off-white, crystalline solid (Scheme 1). 3 TsCN could be applied as an active dienophile as well as a dipolarophile in [2 + 3] cycloaddition or hetero-Diels–Alder reactions. 4 Moreover, it could be applied as a cyanide source, 5 sulfonyl source, 6 or sulfur source 7 in organic reactions.…”

Section: Introductionmentioning

confidence: 99%

Photo-induced radical transformations of tosyl cyanide

Liu,

Li,

Yu

2024

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Stereospecific Oxycyanation of Alkenes with Sulfonyl Cyanide

Kiyokawa

¹

,

Ishizuka

²

,

Minakata

³

2023

Angewandte Chemie

0

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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(C 6 F 5 ) 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(C 6 F 5 ) 3 efficiently activates TsCN through the coordination of the cyano group to the boron center.

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p-Toluenesulfonyl Cyanide

Cited by 3 publications

References 32 publications

Stereospecific Oxycyanation of Alkenes with Sulfonyl Cyanide

Stereospecific Oxycyanation of Alkenes with Sulfonyl Cyanide

Photo-induced radical transformations of tosyl cyanide

Stereospecific Oxycyanation of Alkenes with Sulfonyl Cyanide

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