Department of Chemistry, Shanghai University, 99 Shangda Road, Shanghai, 200444, P. R. China.
Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ, 07102, United States.
Chem Asian J. 2023 Apr 3;18(7):e202201262. doi: 10.1002/asia.202201262. Epub 2023 Feb 20.
In this anniversary issue, we present a DFT study of the mechanism of decarbonylative Hirao cross-coupling of carboxylic-phosphoric anhydrides to afford aryl phosphonates. Traditionally, the direct activation of carboxylic acids to participate in decarbonylative couplings is performed in the presence of carboxylic acid anhydride activators. We discovered that direct dehydrogenative decarbonylative phosphorylation of benzoic acid can be performed in high yield via dehydrogenative and decarbonylative coupling in the presence of phosphite as dual activating and nucleophilic reagent, enabling direct decarbonylative phosphorylation. Control studies demonstrated that carboxylic-phosphoric anhydride (acyl phosphate) is an intermediate in this process. DFT studies were conducted to gain insight into this decarbonylative process and compare the selectivity of C-O and P-O bond activations. Considering the utility of ubiquitous carboxylic acids, this alternative activation pathway may find applications in decarbonylative coupling of carboxylic acids for the synthesis of valuable molecules in organic synthesis.
在本期周年纪念刊中，我们提出了一种 DFT 研究，用于研究羧酸-磷酸酐脱羰 Hirao 交叉偶联反应，以提供芳基膦酸酯。传统上，在羧酸酐活化剂的存在下，通过直接活化羧酸来参与脱羰偶联反应。我们发现，通过亚磷酸酯作为双活化和亲核试剂的存在，通过脱氢和脱羰偶联，可以以高产率进行苯甲酸的直接脱氢脱羰磷酸化，从而实现直接脱羰磷酸化。控制研究表明，羧酸-磷酸酐（酰基磷酸酯）是该过程中的中间体。进行了 DFT 研究以深入了解该脱羰过程，并比较 C-O 和 P-O 键活化的选择性。考虑到普遍存在的羧酸的实用性，这种替代的活化途径可能在羧酸的脱羰偶联反应中找到应用，以合成有机合成中具有价值的分子。
