Accessing 4-oxy-substituted isoquinolinones via C–H activation and regioselective migratory insertion with electronically biased ynol ethers

Abstract

The rhodium-catalyzed C–H activation and annulation with ynol ethers to directly provide 4-oxy substituted isoquinolinones is reported.

Rh(III)‐Catalyzed C−H Activation/Annulation of Aryl Hydroxamates with CF3‐Containing α‐Propargyl α‐Amino Acid Derivatives

“…It is noteworthy that the methyl group placed in ortho ‐position completely suppresses the C−H activation process ( 3 k and 3 l ). The similar phenomenon was previously found for the reaction with internal acetylenes [2d] …”

Synthesis of Functionalized Isoquinolone Derivatives via Rh(III)-Catalyzed [4+2]-Annulation of Benzamides with Internal Acetylene-Containing α-CF3-α-Amino Carboxylates

“…Isoquinolin-1(2 H )-ones and analogues are important nitrogen heterocycles possessing diverse bioactivities and presented in many candidates, including antitumor, anti-diabetic, anti-inflammatory and cardiovascular drugs [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ] ( Figure 1 ). They are also widely used as key intermediates in variety of organic transformations to access more potent bioactive molecules [ 8 , 9 , 10 , 11 , 12 , 13 , 14 ].…”

Access to Substituted Indenol Ethers via a Regioselective Intermolecular Carbopalladation Cascade

“…We recently reported the use of ynol ethers as electronically biased alkynes to control the regioselectivity of migratory insertion and annulation processes en route to 4-oxy-substituted isoquinolinones in the context of a Rh-catalyzed C–H activation reaction (Figure D) . We hypothesized that ynol ethers could control the intermolecular migratory insertion of a Pd–aryl species.…”