Efficient synthesis of isoquinolines in water by a Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids

Abstract

Pd-catalyzed tandem reaction of functionalized alkylnitriles with arylboronic acids for the synthesis of diverse isoquinolines in water.

Comprehensive Strategies for the Synthesis of Isoquinolines: Progress Since 2008

“…[159][160] The mechanism follows a radical pathway which was initiated by the formation of bromodifluoroacetate radical A. Subsequent reactions of A and vinyl isocyanide 28 leads to the formation of cyclohexadienyl radical intermediate C. Again in 2017, Qi et al reported the identical reaction conditions for the successful conversion of 2-(2-oxo-2-arylethyl)benzonitrile 266 with arylboronic acids 197 as reported earlier by Hu et al [157] Additionally, authors have extended scope of this reaction conditions for the synthesis of isoquinolones 268 (Scheme 160). [161] Xiong et al have put forth a Pd-catalyzed C(sp 2 )-H aminoimidoylation of isocyanide vinyl esters 142 towards the synthesis of amino substituted isoquinoline 270.…”

“…Based on these findings, it was proposed that catalytic cycle involves carbopalladation of C(sp 3 )-cyano group followed by intramolecular cyclization (Scheme 158). [157] A similar type of strategy was reported recently by Zhen et al to access aminoisoquinolines and isoquinolones under Nickel-catalyzed reaction conditions. [158] Liu et al reported the synthesis of 1-difluoroalkylated isoquinolines 144 via Pd-catalyzed radical cascade reactions.…”

Nickel‐Catalyzed Tandem Reaction of Functionalized Arylacetonitriles with Arylboronic Acids in 2‐MeTHF: Eco‐Friendly Synthesis of Aminoisoquinolines and Isoquinolones

“…Very recently, our group and others have achieved several tandem transformation of functionalized nitriles with arylboronic acids for access to N ‐heterocycles. For example, palladium‐catalyzed tandem addition/cyclization of 2‐(cyanomethyl)benzonitriles (Scheme b) and methyl 2‐(cyanomethyl)benzoates (Scheme c) with arylboronic acids for the synthesis of isoquinolines and isoquinolones via catalytic carbopalladation of nitriles, respectively. Nickel, as a first‐row transition‐metal in the same group as that of palladium, has attracted significant attention due to its low cost and abundance, meeting the requirements for sustainable chemical synthesis .…”

Efficient Tandem Addition/Cyclization for Access to 2,4-Diarylquinazolines via Catalytic Carbopalladation of Nitriles

“…Therefore, the development of an efficient method that can incorporate the nitrogen atom of nitriles into N -heterocycle products by intramolecular cyclization, rather than hydrolysis of ketamine intermediates, still remains a longstanding challenge. In 2017, we have successfully developed a tandem addition and cyclization strategy for the synthesis of isoquinolines and isoquinolones via catalytic carbopalladation of nitriles [24,25].…”