Aromatic Cyanoalkylation through Double C-H Activation Mediated by Ni(III).
Herein we report an atom- and step-economic aromatic cyanoalkylation reaction that employs nitriles as building blocks and proceeds through Csp(2)-H and Csp(3)-H bond activation steps mediated by Ni(III). In addition to cyanomethylation with MeCN, regioselective α-cyanoalkylation was observed with various nitrile substrates to generate secondary and tertiary nitriles. Importantly, to the best of our knowledge these are the first examples of C-H bond activation reactions occurring at a Ni(III) center, which may exhibit different reactivity and selectivity profiles than those corresponding to analogous Ni(II) centers. These studies provide guiding principles to design catalytic C-H activation and functionalization reactions involving high-valent Ni species.
Department of Chemistry, Washington University , St. Louis, Missouri 63130-4899, United States.
Wen
W
Zhou
Department of Chemistry, Washington University , St. Louis, Missouri 63130-4899, United States.
Shuai
S
Zheng
Department of Chemistry, Washington University , St. Louis, Missouri 63130-4899, United States.
Jason W
JW
Schultz
Department of Chemistry and Biochemistry, University of Missouri-St. Louis , St. Louis, Missouri 63121-4400, United States.
Nigam P
NP
Rath
Department of Chemistry, Washington University , St. Louis, Missouri 63130-4899, United States.
Liviu M
LM
Mirica