64871-66-5Relevant articles and documents
Asmic Isocyanide-Nitrile Isomerization-Alkylations
Alwedi, Embarek,Lujan-Montelongo, J. Armando,Cortés-Mejía, Rodrigo,del Campo, Jorge M.,Altundas, Bilal,Fleming, Fraser F.
supporting information, p. 4644 - 4648 (2019/07/31)
Anisylsulfanylmethylisocyanide, Asmic, is a versatile building block whose alkylations provide a range of substituted isocyanides. The anisylsulfanyl group plays a critical role in the sequenced deprotonation-alkylation and the subsequent sulfanyl-lithium exchange. Complexation of the anisylsulfanyl group to BuLi in the presence of TMEDA affords a lithiated isocyanide whose alkylations generate trisubstituted isocyanides. In the absence of TMEDA, BuLi triggers cyanide expulsion to afford a transient carbene; reorientation of cyanide with attack at the carbene affords a lithiated nitrile whose alkylations afford quaternary nitriles. The complexation-induced isocyanide-nitrile rearrangement is exceptionally facile, occurring within 5 min at –78 °C. Detailed mechanistic and computational analyses identify the importance of chelation in the bifurcating mechanism: internal chelation favors cyanide extrusion to form a carbene whereas chelating agents favor arylsulfanyl-lithium exchange to generate a lithiated isocyanide. The combined experimental and computational analyses reveal a new mechanism for isocyanide-nitrile isomerization which provides valuable insight for rapidly assembling substituted isocyanides.
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.
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
