Cobalt-Catalyzed Carbonylative Cyclization of Pyridinyl Diazoacetates for the Synthesis of Pyridoisoquinolinones

Abstract

Dicobalt octacarbonyl-catalyzed carbonylative cyclization of pyridinyl diazoacetates is developed for the synthesis of pyridoisoquinolinones under mild conditions (room temperature) in a carbon monoxide atmosphere. Moreover, a synthetic method for various pyridoisoquinolinones from ethylpyridinyl aryl acetates is demonstrated through diazotization using TsN3 and DBU followed by Co-catalyzed carbonylation to generate ketene intermediates, which can subsequently undergo intramolecular cyclization under mild conditions in a carbon monoxide atmosphere in a semi-one-pot fashion.

Synthesis of Amido Esters and Amido Phosphonates through Carbonylation of Diazo Compounds Followed by Nucleophilic Addition Reaction

“…[43][44][45] Thus, if we use an organic carbonyl compound as a nongaseous CO source, we will need a separate catalyst to activate the diazo compound and yield the carbene. [47][48][49] For the initial screening of different carbonylmetal compounds, we chose commercially less expensive Co 2 (CO) 8 and Fe 2 (CO) 9 as solid CO sources. Herein, we have chosen carbonylmetal compounds as a nongaseous carbon monoxide source.…”

Copper‐Catalyzed Carbonyl Group Controlled Coupling of Isatin Oximes with Arylboronic Acids To Prepare N‐Aryloxindole Nitrones

“…Next, we pursued the preparation of more complex N ‐arylisatin nitrones by using this efficient copper‐catalyzed N ‐arylation strategy. As shown in Scheme , estrone‐derived arylboronic acid 2u was easily prepared by Lee's method in three steps . When arylboronic acid 2u and isatin oxime 1a were combined under the copper‐mediated reaction conditions, the desired estrone‐derived nitrone 3au was afforded in 81 % yield.…”

Diazo Compounds: Versatile Synthons for the Synthesis of Nitrogen Heterocycles via Transition Metal‐Catalyzed Cascade C–H Activation/Carbene Insertion/Annulation Reactions

“…[45] In addition,t he transformation could be achieved in a semi-one-pot fashion from the corresponding pyridinyl aryl esters 72 through diazotization in the presence of TsN 3 and DBU( Scheme 36). [45] In addition,t he transformation could be achieved in a semi-one-pot fashion from the corresponding pyridinyl aryl esters 72 through diazotization in the presence of TsN 3 and DBU( Scheme 36).…”

“…Rhodium-catalyzed C-H activation of N-Bochydrazones. [45] C-H activation/cyclization sequence of N-methoxybenzamides 80 with a-diazotized Meldrumsa cid for the synthesis of diverse N-methoxyisoquinolinediones 81 (Scheme 39). Cobalt-catalyzed carbenoid insertion into N-heteroarylarenes.…”

“…Rhodium-catalyzed annulation of primary benzamides. [45] Scheme 37. Rhodium-catalyzed carbenoid insertioni nto Nmethoxybenzamides.…”