Cobalt-catalyzed carbonylation of the C–H bond

Abstract

Direct carbonylation of the C–H bond is a great tool for installing a carbonyl group in a wide variety of substrates.

Cobalt-Catalyzed C(sp2)–H Carbonylation of Amino Acids Using Picolinamide as a Traceless Directing Group

“…In recent years, a number of carbonylation methods have been developed using cobalt catalysis. 9 However, most of them can only be applied to aliphatic amide or benzamide type substrates. To date, there are no literature examples for direct carbonylation of phenylalanine type substrates using first-row TM catalysis.…”

Visible‐Light‐Driven Isocyanide Insertion to o‐Alkenylanilines: A Route to Isoindolinone Synthesis

“…The use of organic dyes such as eosin B, Rose Bengal, and Rhodamine B (Table 1, entries 3-5) gave inferior yields compared to eosin Y. Screening of other inorganic bases, such as Na 2 CO 3 , K 2 CO 3 , and t BuOK, instead of Cs 2 CO 3 had a detrimental influence on the yield (Table 1, entries 6- 8). Similarly, the use of organic base DMAP failed to improve the product yield (Table 1, entry 9).…”

“…[4] The prerequisite isoindolinone derivatives are synthesized via lactamization of o-(aminomethyl)benzoic acids, [5] reductive/condensative cyclizations, [6] halogenation (or direct CÀ H activation) and cyclization of omethylbenzamides, [7] and carbonylative strategies {Scheme 1 (i)}. [8] The CÀ H functionalization strategies for isoindolinone synthesis requires the use of Nsubstituted benzamides as reactants bearing either activating or directing groups {Scheme 1 (ii)}. [9] The common synthetic precursor for the synthesis of isoindolinone is N-substituted benzamides which are synthesized via carbonylative coupling using aryl halides or aryl diazonium salts as electrophile and primary or secondary amines as nucleophiles.…”

Traceless Directing Groups in Sustainable Metal-Catalyzed C–H Activation

“…The first DG used in cobalt-catalyzed C-H functionalization was an imine group, facilitating the C-H carbonylation at the ortho position of the substrate, using high pressures of carbon monoxide and Co 2 (CO) 8 [97]. This early report by Murahashi and co-workers showcased the potential of cobalt in C-H carbonylation, a transformation in which cobalt catalysis still holds a prominent position [98], notably by also utilizing TDGs. In general, cobalt has become one of the most broadly studied transition metals in C-H activation [39,95,96] and its modes of action are well understood [50], as exemplified by the rational design and use of ligands in many cases [39,95,96,99].…”