Lin Zechao, Li Jiahong, Huang Qingfei, Huang Qiuya, Wang Qiwei, Tang Lei, Gong Deying, Yang Jun, Zhu Jin, Deng Jingen
†Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China.
§Graduate University of Chinese Academy of Sciences, Beijing 100049, China.
J Org Chem. 2015 May 1;80(9):4419-29. doi: 10.1021/acs.joc.5b00241. Epub 2015 Apr 13.
A series of amphiphilic ligands were designed and synthesized. The rhodium complexes with the ligands were applied to the asymmetric transfer hydrogenation of broad range of long-chained aliphatic ketoesters in neat water. Quantitative conversion and excellent enantioselectivity (up to 99% ee) was observed for α-, β-, γ-, δ- and ε-ketoesters as well as for α- and β-acyloxyketone using chiral surfactant-type catalyst 2. The CH/π interaction and the strong hydrophobic interaction of long aliphatic chains between the catalyst and the substrate in the metallomicelle core played a key role in the catalytic transition state. Synergistic effects between the metal-catalyzed site and the hydrophobic microenvironment of the core in the micelle contributed to high stereoselectivity.
设计并合成了一系列两亲性配体。将带有这些配体的铑配合物应用于在纯水中对多种长链脂肪族酮酯的不对称转移氢化反应。使用手性表面活性剂型催化剂2时，观察到α-、β-、γ-、δ-和ε-酮酯以及α-和β-酰氧基酮实现了定量转化和优异的对映选择性（高达99% ee）。金属胶束核心中催化剂与底物之间的CH/π相互作用以及长脂肪链的强疏水相互作用在催化过渡态中起关键作用。胶束中金属催化位点与核心疏水微环境之间的协同效应有助于实现高立体选择性。
