Palladium‐Catalyzed Alkynylcarbonylation of Aryl Iodides with the Use of Mo(CO)₆ in the Presence of tBu₃P Ligand

Abstract

Palladium‐catalyzed alkynylcarbonylation of aryl iodides was accomplished by using Mo(CO)6 as a CO source. The reaction was conducted at room temperature with the use of tBu3P as a ligand, which was found to be essential for smooth carbonylation. One‐pot construction of pyrazoles by using aryl iodides with electron‐withdrawing groups was also accomplished under these reaction conditions in the presence of methylhydrazine. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Phosphine-free NiBr2-catalyzed synthesis of unsymmetrical diaryl ketones via carbonylative cross-coupling of aryl iodides with Ph3SnX (X = Cl, OEt)

“…Therefore, NiBr 2 was applied as the catalyst for this transformation. Applying different bases in DMF showed that the reaction worked well in the presence of K 2 CO 3 ( Table 1, entries [10][11][12]. The efficient amount of Ph 3 SnCl was found to be 0.4 equiv for 1.0 mmol of 4-iodotoluene.…”

“…In addition, due to the difficulty of handling of gaseous CO, a suitable substituent for CO is of great interest [10]. In this regard, the application of metal carbonyls [11] and organic compounds [12] having carbonyl in their structure have been developed.…”

Palladium‐Catalysed Multicomponent Aminocarbonylation of Aryl or Heteroaryl Halides with [Mo(CO)6] and Aryl‐ or ­Heteroarylamines Using Conventional Heating

“…[9] They also used tBu 3 P in the palladium-catalysed [Pd(tBu 3 P) 2 ]-alkynylcarbonylation of aryl iodides with phenylacetylene and [Mo(CO) 6 ] in the presence of CH 3 CN and Et 3 N at room temperature. [10] Herein we report the use of [Mo(CO) 6 ] in the multicomponent palladium-assisted aminocarbonylation of electrondeficient and -rich heteroaryl halides and iodoanisole with several (hetero)arylamines to give the corresponding di-(hetero)arylamides using conventional heating for 1-3 h, thus extending the scope of this reaction. Palladium acetate was used as the palladium source with the (hetero)aryl iodides and trans-di-µ-acetatobis [2-(di-o-tolylphosphanyl)benzyl]dipalladium(II), also known as "Herrmann's palladacycle", [11,12] was used with the (hetero)aryl bromides.…”

Easy‐to‐Execute Carbonylative Arylation of Aryl Halides using Molybdenum Hexacarbonyl: Efficient Synthesis of Unsymmetrical Diaryl Ketones

“…In this regard, molybdenum hexacarbonyl was previously identified as an easily handled solid reagent for the in situ release of carbon monoxide upon heating in sealed vessels. It has been proven to enable the fast development of new easy-to-execute carbonylation protocols and depending on the nucleophiles employed, aromatic esters, [20] amides, [21] carboxylic acids, [20,21a] sulfonimides, [22] and alkynyl ketones [23] were smoothly obtained. Furthermore, it has also been employed in double carbonylation of aryl iodides in the presence of tBu 3 P as a ligand.…”