Murayama Sei, Li Zhurong, Liang Huatai, Liu Yan, Naka Hiroshi, Maruoka Keiji
Graduate School of Pharmaceutical Sciences, Kyoto University, Kyoto, 606-8501, Japan.
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, 510006, P. R. China.
Chemistry. 2023 Sep 21;29(53):e202301866. doi: 10.1002/chem.202301866. Epub 2023 Jul 28.
Site-specifically deuterated organocatalysts were prepared and found to show improved reactivity over the non-deuterated analogs. Two privileged C -symmetric chiral binaphthyl-modified tetraalkylammonium salts were selected for this study. The stability of these phase-transfer catalysts was generally improved by site-specific deuteration, though the degree of improvement was structure dependent. In particular, a large secondary kinetic isotope effect was observed for the tetradeuterated phase-transfer catalyst. The performance of these deuterated catalysts in the asymmetric catalytic alkylation of amino acid derivatives was better than that of non-deuterated analogs at low catalyst loadings. The results suggest that catalyst deuteration is a promising strategy for enhancing the stability and performance of organocatalysts.
制备了位点特异性氘代有机催化剂，发现其比未氘代的类似物表现出更高的反应活性。本研究选择了两种具有优势的C-对称手性联萘修饰的四烷基铵盐。这些相转移催化剂的稳定性通常通过位点特异性氘代得到提高，尽管提高程度取决于结构。特别地，观察到四氘代相转移催化剂有较大的二级动力学同位素效应。在低催化剂负载量下，这些氘代催化剂在氨基酸衍生物的不对称催化烷基化反应中的性能优于未氘代的类似物。结果表明，催化剂氘代是提高有机催化剂稳定性和性能的一种有前景的策略。
