Santi Nicolò, Morrill Louis C, Swiderek Katarzyna, Moliner Vicent, Luk Louis Y P
School of Chemistry, Main Building, Cardiff University, Cardiff CF10 3AT, UK.
Departament de Química Física i Analítica, Universitat Jaume I, Castelló 12071, Spain.
Chem Commun (Camb). 2021 Feb 23;57(15):1919-1922. doi: 10.1039/d0cc08142f.
Here, the streptavidin-biotin technology was applied to enable organocatalytic transfer hydrogenation. By introducing a biotin-tethered pyrrolidine (1) to the tetrameric streptavidin (T-Sav), the resulting hybrid catalyst was able to mediate hydride transfer from dihydro-benzylnicotinamide (BNAH) to α,β-unsaturated aldehydes. Hydrogenation of cinnamaldehyde and some of its aryl-substituted analogues was found to be nearly quantitative. Kinetic measurements revealed that the T-Sav:1 assembly possesses enzyme-like behavior, whereas isotope effect analysis, performed by QM/MM simulations, illustrated that the step of hydride transfer is at least partially rate-limiting. These results have proven the concept that T-Sav can be used to host secondary amine-catalyzed transfer hydrogenations.
在此，应用链霉亲和素-生物素技术实现有机催化转移氢化反应。通过将生物素连接的吡咯烷（1）引入四聚体链霉亲和素（T-Sav），所得的杂化催化剂能够介导氢化物从二氢苄基烟酰胺（BNAH）转移至α,β-不饱和醛。肉桂醛及其一些芳基取代类似物的氢化反应几乎是定量的。动力学测量表明，T-Sav:1组装体具有类似酶的行为，而通过量子力学/分子力学（QM/MM）模拟进行的同位素效应分析表明，氢化物转移步骤至少部分是限速步骤。这些结果证明了T-Sav可用于承载仲胺催化的转移氢化反应这一概念。
