Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles

Christian A. Malapit, Donald R. Caldwell, Irungu K. Luvaga, Jonathan T. Reeves*, Ivan Volchkov, Nina C. Gonnella, Zhengxu S. Han, Carl A. Busacca, Amy R. Howell, Chris H. Senanayake

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

15 Scopus citations


β-Ketonitriles bearing a quaternary carbon at the 2-position were prepared through Rh-catalyzed addition of aryl boronic acids to 2,2-disubstituted malononitriles. In contrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles, the present reaction avoids retro-Thorpe collapse of the intermediate addition product through the use of a milder base. The reaction was amenable to a variety of aryl boronic acids and disubstituted malononitriles, providing a diverse array of β-ketonitriles. The products could be further derivatized to valuable chiral α,α-disubstituted-β-aminonitriles through addition reactions to the corresponding N-tert-butanesulfinyl imines.

Original languageEnglish (US)
Pages (from-to)6999-7002
Number of pages4
JournalAngewandte Chemie - International Edition
Issue number24
StatePublished - Jun 6 2017
Externally publishedYes


  • boronic acids
  • homogeneous catalysis
  • rhodium
  • sulfinimines
  • β-ketonitriles

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)


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