22156-54-3Relevant academic research and scientific papers
Transition metal-free direct dehydrogenative arylation of activated C(sp3)-H bonds: Synthetic ambit and DFT reactivity predictions
Lovato, Kaitlyn,Guo, Lirong,Xu, Qing-Long,Liu, Fengting,Yousufuddin, Muhammed,Ess, Daniel H.,Kürti, László,Gao, Hongyin
, p. 7992 - 7999 (2018/11/03)
A transition metal-free dehydrogenative method for the direct mono-arylation of a wide range of activated C(sp3)-H bonds has been developed. This operationally simple and environmentally friendly aerobic arylation uses tert-BuOK as the base and nitroarenes as electrophiles to prepare up to gram quantities of structurally diverse sets (>60 examples) of α-arylated esters, amides, nitriles, sulfones and triaryl methanes. DFT calculations provided a predictive model, which states that substrates containing a C(sp3)-H bond with a sufficiently low pKa value should readily undergo arylation. The DFT prediction was confirmed through experimental testing of nearly a dozen substrates containing activated C(sp3)-H bonds. This arylation method was also used in a one-pot protocol to synthesize over twenty compounds containing all-carbon quaternary centers.
Oxidative nucleophilic substitution of hydrogen in nitroarenes with phenylacetonitrile derivatives
Makosza, Mieczyslaw,Stalinski, Krzysztof
, p. 8797 - 8810 (2007/10/03)
Tertiary carbanions generated from α-substituted phenylacetonitriles in liquid ammonia add to nitrobenzenes in the para position to form the corresponding σ(H)-adducts which are transformed, depending on the starting nitriles and the reaction conditions, to products of oxidative nucleophilic substitution of hydrogen, ONSH or vicarious nucleophilic substitution, VNS.
