Direct synthesis of 2-substituted benzonitriles via alkylcyanation of arynes with N,N-disubstituted aminomalononitriles

Abstract

<p>An efficient alkylcyanation of <italic>in situ</italic> generated arynes by <italic>N</italic>,<italic>N</italic>-disubstituted aminomalononitriles is described, enabling the direct synthesis of 2-substituted benzonitriles.</p>

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

“…496 Recently, Wang and co-workers demonstrated that aryne alkylcyanation could take place with N,N-disubstituted aminomalononitriles 7-26, giving rise to 2-substituted benzonitriles 7-27 in moderate to high yields (Scheme 96c). 497 β-Keto sulfones were found to be suitable substrates for this C−C bond insertion protocol as well. In 2008, the groups of Huang 498 and Hu 416 independently demonstrated that β-keto sulfones 7-28 could participate in aryne insertion reaction to (phenylsulfonyl)acetophenone (7-30) was employed to produce acyl-fluoroalkylated arenes 7-31 in good to high yields (Scheme 97a).…”

“…In 2007, the same group accomplished double aryne insertion cascade processes from either α-Ts nitrile or dinitrile compounds 7-22 , which led to the formation of diarylmethane skeleton 7-23 through a sequential C–CN bond insertion/C-arylation via intermediates 7-24 and 7-25 , respectively (Scheme b) . Recently, Wang and co-workers demonstrated that aryne alkylcyanation could take place with N , N -disubstituted aminomalononitriles 7-26 , giving rise to 2-substituted benzonitriles 7-27 in moderate to high yields (Scheme c) …”