36638-55-8Relevant academic research and scientific papers
Sulfone–Metal Exchange and Alkylation of Sulfonylnitriles
Yang, Xun,Nath, Dinesh,Gau, Michael R.,Steward, Omar W.,Fleming, Fraser F.
supporting information, p. 7257 - 7260 (2017/06/13)
The first general sulfone–metal exchange is described. Treating substituted 2-pyridylsulfonylacetonitriles with either BuLi or Bu3MgLi generates metalated nitriles that efficiently intercept a variety of electrophiles to afford quaternary nitriles. The 2-pyridylsulfone is critical for the sulfone–metal exchange because chelation anchors the organometallic proximal to the electrophilic, tetrasubstituted sulfone to override complex-induced deprotonation. Alkylating commercial 2-pyridinesulfonylacetonitrile with mild bases, either K2CO3 or DBU, and subsequent sulfone–metal exchange and alkylation rapidly assembles quaternary nitriles by three alkylations, only one of which requires an organometallic reagent.
Arylthio-metal exchange of α-arylthioalkanenitriles
Nath, Dinesh,Skilbeck, Melanie C.,Coldham, Iain,Fleming, Fraser F.
supporting information, p. 62 - 65 (2014/01/23)
The addition of BuLi, Bu3MgLi, Et2ZnBuLi, or Me 2CuLi to α-arylthioalkanenitriles triggers an arylthio-metal exchange. NMR spectroscopic analyses implicate organometallic attack on sulfur forming a three-coordinate sulfidate as the key intermediate. Electrophilic trapping affords tertiary and quaternary nitriles in high yield. The method addresses the challenge of improving the functional group tolerance and preventing polyalkylations.
Sulfinylnitriles: Sulfinyl-metal exchange-alkylation strategies
Nath, Dinesh,Fleming, Fraser F.
, p. 2023 - 2029 (2013/03/14)
Adding organolithiums, Grignard reagents, or zincates to sulfinylnitriles triggers a facile sulfinyl-metal exchange to afford N- or C-metalated nitriles. Sulfinyl-magnesium exchange-alkylations efficiently install quaternary and tertiary centers, even in
Nitrile alkylations through sulfinyl-metal exchange
Nath, Dinesh,Fleming, Fraser F.
, p. 11790 - 11793 (2012/01/06)
Triple alkylation: Phenylsulfinyl- and phenylthioacetonitrile can function as trianion equivalents of acetonitrile by sequential alkylation and sulfinyl-metal exchange (see scheme; mCPBA=meta-chloroperoxybenzoic acid). The metalated nitriles alkylate a range of electrophiles to obtain nitriles with quaternary centers. The sulfinyl-metal exchange proceeds under very mild conditions and has a high functional-group tolerance. Copyright
α-(Benzotriazolyl)methyl phenyl thioethers: Convenient reagents for α-phenylthioalkylation of silylated nucleophiles
Katritzky, Alan R.,Chen, Jie,Belyakov, Sergei A.
, p. 6631 - 6634 (2007/10/03)
Stable, crystalline α-(benzotriazolyl)methyl phenyl thioethers (1), easily prepared from carbonyl compounds, thiophenol and benzotriazole, are convenient reagents for the phenylthiomethylation of trimethylsilyl cyanide, trimethylallylsilane, and trimethyl
A Convenient Method for the Transformation of Alkenyl Sulfides to 2-(Phenylthio)alkanenitriles, Homoallyl Sulfides, and Thioacetals
Takeda, Takeshi,Kaneko, Yuichiro,Nakagawa, Hitoshi,Fujiwara, Tooru
, p. 1963 - 1966 (2007/10/02)
2-(Phenylthio)alkanenitriles, homoallyl sulfides, and thioacetals were obtained in good yields by the reaction of alkenyl sulfides with the corresponding silyl nucleophiles via thionium ion intermediates.
