Palladium-Catalyzed Norbornene-Mediated Tandem Amination/Cyanation Reaction: A Method for the Synthesis of ortho-Aminated Benzonitriles

Abstract

A palladium-catalyzed, norbornene-mediated tandem amination/cyanation reaction via Catellani-type C-H functionalization was developed using N-benzoyloxyamines as the amination reagent and Zn(CN)2 as the terminating agent. This transformation, in which one C-N bond and one C-C bond are formed, provides an efficient approach for the synthesis of ortho-aminated benzonitriles in one pot from easily accessible starting materials.

Copper‐Catalyzed Deoxygenative C‐2 Amination of Quinoline N‐Oxides

“…Initially, a model reaction between quinoline N ‐oxide ( 1a ) and O ‐benzoyl hydroxylamine ( 2a ) was selected to explore the reaction conditions in the presence of Cu(OAc) 2 as catalyst. However, neither 3a nor 3a′ was detected as the model reaction was performed in THF (Table , entry 1).…”

Regioselective Synthesis of Polycyclic and Heptagon‐embedded Aromatic Compounds through a Versatile π‐Extension of Aryl Halides

“…However,s ymmetrical pextension fragment or coupling partners were used and regioselectivity was not fully demonstrated. [10] Their unselective insertions to the metal center are difficult to control with an ancillary ligand and mostly give isomeric mixtures that are inseparable.W eare highly interested in the development of cross-coupling reactions [11] for material science and we realized that domino reactions [12] such as norbornene(NBE)-mediatedp alladium cascades [13] hold great potential for not only tackling the sequential reactions in one pot, but also providing access to the ubiquitous aryl halides.However,the homo-coupling of aryl halides might be facile,w hile directing groups,w hich assist in the controlled heterobiaryl coupling,m ight be difficult to be removed after reactions. [10] Their unselective insertions to the metal center are difficult to control with an ancillary ligand and mostly give isomeric mixtures that are inseparable.W eare highly interested in the development of cross-coupling reactions [11] for material science and we realized that domino reactions [12] such as norbornene(NBE)-mediatedp alladium cascades [13] hold great potential for not only tackling the sequential reactions in one pot, but also providing access to the ubiquitous aryl halides.However,the homo-coupling of aryl halides might be facile,w hile directing groups,w hich assist in the controlled heterobiaryl coupling,m ight be difficult to be removed after reactions.…”

Norbornene in Organic Synthesis

“…The introduction of other groups as well as an amine group was also reported by the Chen, 161 Gu, 162 Chen/Wu, 163 and Lautens 164,165 groups. Selected examples are shown in Scheme 74.…”