Activating Group Recycling in Action: A Rhodium-Catalyzed Carbothiolation Route to Substituted Isoquinolines
نویسندگان
چکیده
A new rhodium(I) catalyst allows practical and efficient alkyne carbothiolation reactions to be achieved on synthetically useful ketone-bearing aryl methyl sulfides. The carbothiolation adducts, featuring a 'recycled methyl sulfide' activating group, are convenient precursors to highly substituted isoquinolines.
منابع مشابه
Isoquinoline synthesis via rhodium-catalyzed oxidative cross-coupling/cyclization of aryl aldimines and alkynes.
A general rhodium-catalyzed oxidative coupling reaction between internal alkynes and aryl aldimines is described. This process affords 3,4-disubstituted isoquinolines in good yield and high regioselectivity. Preliminary mechanistic studies suggest that the C-N bond formation arises from the reductive elimination of a rhodium(III) species.
متن کاملRh(III)-Catalyzed Decarboxylative Coupling of Acrylic Acids with Unsaturated Oxime Esters: Carboxylic Acids Serve as Traceless Activators
α,β-Unsaturated carboxylic acids undergo Rh(III)-catalyzed decarboxylative coupling with α,β-unsaturated O-pivaloyl oximes to provide substituted pyridines in good yield. The carboxylic acid, which is removed by decarboxylation, serves as a traceless activating group, giving 5-substituted pyridines with very high levels of regioselectivity. Mechanistic studies rule out a picolinic acid intermed...
متن کاملRhodium-Catalyzed C-H Annulation of Nitrones with Alkynes: A Regiospecific Route to Unsymmetrical 2,3-Diaryl-Substituted Indoles.
The direct C-H annulation of anilines or related compounds with internal alkynes provides straightforward access to 2,3-disubstituted indole products. However, this transformation proceeds with poor regioselectivity in the synthesis of unsymmetrically 2,3-diaryl substituted indoles. Herein, we report the rhodium(III)-catalyzed C-H annulation of nitrones with symmetrical diaryl alkynes as an alt...
متن کاملSynthesis of substituted isoquinolines utilizing palladium-catalyzed α-arylation of ketones.
The utilization of sequential palladium-catalyzed α-arylation and cyclization reactions provides a general approach to an array of isoquinolines and their corresponding N-oxides. This methodology allows the convergent combination of readily available precursors in a regioselective manner and in excellent overall yields. This powerful route to polysubstituted isoquinolines, which is not limited ...
متن کاملRhodium(iii)-catalyzed annulation of arenes with alkynes assisted by an internal oxidizing N-O bond.
Rh(iii)-catalyzed C-H activation of 3-aryl-dihydroisoxazoles in the coupling with diarylacetylenes has been developed under redox-neutral conditions. This reaction occurred under mild conditions with no by-product, and the N-O bond functions as an oxidizing directing group, leading to efficient synthesis of isoquinolines functionalized with a proximal secondary alcohol.
متن کامل