Amino- and azidocarbonylation of iodoalkenes

Synthesis of Novel Cavitand Host Molecules via Palladium-Catalyzed Aryloxy- and Azidocarbonylation

“…The formation of cavitand 13 can be explained by the Curtius rearrangement of the acylazide to isocyanate, followed by the reaction with traces of water. It is worth noting that primary amides with various structures could be isolated as main products from an azidocarbonylation reaction when aqueous biphasic solvent mixtures were used [ 33 ]. The other solution proposed by Grushin et al to achieve 100% conversion, the use of a two-phase solvent system, was not applicable, since the cavitand substrate does not dissolve in apolar solvents.…”

“…Grushin’s seminal work on palladium-catalyzed azidocarbonylation of iodoaromatic compounds was published in 2012; that is why it is not considered strange (unlike aryloxycarbonylation) that on macromolecules, to the best of our knowledge, it has not yet been applied. Some sporadic results were published on the use of azide as a N -nucleophile in palladium-catalyzed homogeneous catalytic reactions [ 31 , 32 , 33 , 34 ], revealing the high reactivity of acyl azides. Primary carboxamides as stable final products were obtained using this protocol.…”

Alkyl Levulinates and 2-Methyltetrahydrofuran: Possible Biomass-Based Solvents in Palladium-Catalyzed Aminocarbonylation

“…Carboxamides can be synthesized from easily available starting materials with aminocarbonylation, although the conventional carboxylic acid−carboxylic halide−carboxamide route is difficult to prepare because it has no notable yield in the implementation [ 29 , 30 ]. Moreover, our research group has been investigating this reaction in the conventional solvent DMF for years [ 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 ], and thanks to the ascertainments of the groups from Skrydstrup [ 40 ] and Mika [ 41 , 42 , 43 ], our interest has been turned to the investigation of green solvents.…”