Fossil-based solvents and triethylamine as a toxic and volatile base were successfully replaced with γ-valerolactone as a non-volatile solvent and K₂CO₃ as inorganic base in the alkoxy- and aryloxycarbonylation of aryl iodides using phosphine-free Pd catalyst systems. By this, the traditional systems were not simply replaced but also significantly improved. In the study, the effects of different reaction parameters, i.e. the use of several other solvents, the temperature, the carbon monoxide pressure, the base and the catalyst concentrations, were evaluated in details on the efficiency of the carbonylations. To gather some information on the mechanism of these reactions, the effects of electronic parameters (σ) of various aromatic substituents of the aryl iodides as well as the influence of para-substitution of phenol were investigated on the activity. For a comparison, the aryl-substituted aryl iodides were also reacted with methanol and aryl iodide was also alkoxycarbonylated using several different lower alcohols. From the observed correlations between the electronic parameters of the aromatic substituents and the rates, it appears that the rate determining step is the oxidative addition of Ar–I to Pd⁰, provided that sufficient amounts of nucleophiles are present for the ester formation. If this is not the case, the rate of nucleophile attack might determine the overall rate.

基于化石的溶剂和三乙胺作为有毒和挥发性碱被成功地替换为γ -戊内酯作为非挥发性溶剂和K ₂ CO ₃使用无膦的Pd催化剂体系在芳基碘化物的烷氧基羰基化和芳氧基羰基化中用作无机碱。这样，传统的系统不仅被简单地替换，而且得到了显着改善。在研究中，详细评估了羰基化效率对不同反应参数（即使用其他几种溶剂，温度，一氧化碳压力，碱和催化剂浓度）的影响。为了收集有关这些反应机理的一些信息，研究了芳基碘化物的各种芳族取代基的电子参数（σ）的影响以及苯酚的对位取代对活性的影响。为了比较，芳基取代的芳基碘化物也与甲醇反应，芳基碘化物也用几种不同的低级醇烷氧基羰基化。从所观察到的芳族取代基的电子参数与速率之间的相关性来看，速率确定步骤似乎是将Ar–I氧化添加到Pd中⁰，前提是存在足够量的亲核试剂以形成酯。如果不是这种情况，亲核试剂的攻击速率可能决定总体速率。