Convenient Stille carbonylative cross-couplings using molybdenum hexacarbonyl

5-Bromo-norborn-2-en-7-one derivatives as a carbon monoxide source for palladium catalyzed carbonylation reactions

“…Entry 4, Table 3 shows the synthesis of a model system that involved the synthesis of simpler aryl iodide component 6f reacting with 4-chlorophenylboronic acid (14b) to give the corresponding biaryl ketone 15d in 75% yield. In a similar Table 2 Palladium-catalysed aminocarbonylation reactions carried out with aryl iodides 6a-e and morpholine (9). All reactions were carried out at 100 C for 20 hours in a sealed two-chamber apparatus Table 3).…”

“…In early work, the most commonly used CO sources were metal carbonyl compounds such as Mo(CO) 6 which proved useful, among others, for palladium catalysed aminocarbonylations and carbonylative Stille reactions of aryl halides. [7][8][9] Recently, we have reported the development of norborneneone derivatives such as oCOm-21 as physiologically relevant carbon monoxide releasing molecules. This water soluble Carbon Monoxide Releasing Molecule (CORM) undergoes an E1 cB elimination of HBr to a norbornadienone intermediate that spontaneously undergoes cheletropic release of CO in TRISsucrose buffer at pH 7.4 at 37 C with a half-life of 19 minutes (Scheme 1).…”

Palladium‐catalysed reductive carbonylation of aryl halides with iron pentacarbonyl for synthesis of aromatic aldehydes and deuterated aldehydes

“…[14] In 2013, Skrystrup and co-workers demonstrated that D-isotopelabelled aldehydes can be achieved via Pd-catalysed carbonylation in a sealed two-chamber system applying 9-methylfluorene-9carbonyl chloride as a source of externally delivered CO and DCO 2 K for deuterium labelling. [15] Besides gaseous CO, metal carbonyls have also been used as the CO source for carbonylative insertion reactions such as amidation, [16] esterification, [17] alkenylcarbonylation, [18] Stille reaction [19] and carbonylative arylation. [20] In addition, carbonylation of iodoarenes in the presence of gaseous CO has been done using bimetallic catalytic systems like Fe(CO) 5 -Co 2 (CO) 8 in which the metal carbonyl system was not the CO source for the reaction.…”

Carbonylative annulation of unsaturated compounds using molybdenum hexacarbonyl: an efficient synthesis of 2(1H)-quinolones

“…In this regard, several groups have reported on various CO-gas free methods including microwave-assisted palladium-catalyzed Mo(CO) 6 -mediated carbonylative coupling reactions. [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] Recently we also reported a facile route to diaryl ketones through palladium-catalyzed three-component cross-coupling of aryl and heteroaryl halides, Mo(CO) 6 and boronic acids and offered a mild base/solvent combination for efficient microwave-free extrusion of carbon monoxide in the course of the reaction. 33 Continuing our interest in carbonylation reactions, we further attempted to synthesize (dihydro)quinolones via carbonylative annulation reactions of readily available 2-iodoanilines and unsaturated compounds.…”