Palladium‐Catalyzed Aromatic Azidocarbonylation

Palladium‐Catalyzed Intermolecular Oxidative Diazidation of Alkenes

“…However, Canty et al [9] disclosed that the reductive elimination of LPd IV Me 2 (N 3 ) only gave Pd(II)-N 3 and ethane. Later, Grushin et al [10,11] reported that the reductive elimination of Pd(II)-N 3 complexes only occurred in the case of steric bulky ligand, such as Xantphos. In order to give insight on this point, an alkyl-Pd-N 3 complex 7 was synthesized through ligand exchange, and employed to survey the azidation reaction.…”

Synthesis of Acylphosphonates by a Palladium‐Catalyzed Phosphonocarbonylation Reaction of Aryl Iodides with Phosphites

“…Initially, the phenylpalladium complex 4 was prepared from Pd 2 (dba) 3 ⋅CHCl 3 (dba=1,5‐diphenyl‐1,4‐pentadien‐3‐one), XANTPHOS (1 equiv), and 1 a (1 equiv) according to the reported method 20. Treatment of a CD 2 Cl 2 solution of 4 with carbon monoxide gave rise to benzoylpalladium iodide 5 in quantitative yield, as previously reported 8. When the benzoylpalladium complex 5 was treated with diethyl phosphite at room temperature under a nitrogen atmosphere, the expected palladium–phosphonate complex 6 was not observed.…”

Recyclable Polymer-Supported Terpyridine–Palladium Complex for the Tandem Aminocarbonylation of Aryl Iodides to Primary Amides in Water Using NaN3 as Ammonia Equivalent

“…Firstly, we examined the aminocarbonylation in water according to the reported procedures [22]. Thus, the aminocarbonylations of iodobenzene (2a) and NaN 3 (3) were carried out in water with PMHS as reducing agent for the generated benzoyl azide in the presence of the polymeric catalyst 1 (5 mol % to Pd) at 50 • C for 8 h under 5 atm of CO gas.…”

“…Although sodium azide is highly toxic, it is ease to handle because it is not gaseous, and it has advantage that it can be handled stably in water. There is only one reported example of a Pd/Xantphos catalyzed azidocarbonylation reaction in tetrahydrofuran (THF)-producing benzoyl azide products, and this was not performed with the aim of synthesizing primary amines [22].…”