Synthesis of Polycyclic Benzonitriles via a One-Pot Aryl Alkylation/Cyanation Reaction

Abstract

A norbornene-mediated palladium-catalyzed tandem alkylation/cyanation sequence is described in which an alkyl-aryl bond and a nitrile-aryl bond are formed in one pot. A variety of sterically hindered, five-, six-, and seven-membered ring benzonitriles were synthesized in good yields from easily accessible starting materials.

Sequential Copper(I)‐Catalyzed Reaction of Amines with o‐Acetylenyl‐Substituted Phenyldiazoacetates

“…CuA C H T U N G T R E N N U N G (MeCN) 4 PF 6 was found to effectively catalyze diazo decomposition, and the subsequent N À H insertion and alkyne hydroamination (entry 1). The reaction gave isoindole 3a through 5-exo-dig cyclization.…”

“…A series of substituted N À H insertion products 11b-h was then prepared by similar reactions catalyzed by Rh 2 A C H T U N G T R E N N U N G (OAc) 4 . The N À H insertion products were subsequently subjected to catalysis by CuA C H T U N G T R E N N U N G (MeCN) 4 PF 6 .…”

“…While efficiency and selectivity are the major concerns in these metal-catalyzed reactions, an emerging area of research in this field is to develop reaction systems in which a single catalyst mediates two or more different reactions in a selective manner. [1][2][3][4] Such a kind of sequential or concurrent catalysis is particularly attractive in organic synthesis in view of ecological and economical concerns in the fine chemical industries. Because there are many different reactions that can be catalyzed by the same or similar transition metal catalysts, a great potential exists to link these reactions in sequence.…”

“…Because there are many different reactions that can be catalyzed by the same or similar transition metal catalysts, a great potential exists to link these reactions in sequence. Recently, a number of efficient sequential catalytic processes, such as Ru-catalyzed RCM/hydrogenation, [2] Rh-catalyzed allylic alkylation/Pauson-Khand reaction, [3] Pd-catalyzed aryl alkylation/cyanation reaction, [4] have been developed. C À N bond formation is important in organic synthesis, and there have been many reports on transition metal-catalyzed C À N bond formations.…”

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Abstract: A highly efficient, tetrakis(acetonitrile)- 4 PF 6 ]-catalyzed tandem Cu(I)-carbene N À H insertion/ Cu(I)-catalyzed hydroamination of alkynes, which leads to sequential formation of two C À N bonds to yield isoindole derivatives, has been developed.

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