Huvelle Steve, Alouane Ahmed, Le Saux Thomas, Jullien Ludovic, Schmidt Frédéric
Institut Curie, PSL Research University, CNRS UMR3666, INSERM U1143, 26 rue d'Ulm, F-75005, Paris, France.
Org Biomol Chem. 2017 Apr 18;15(16):3435-3443. doi: 10.1039/c7ob00121e.
Kinetic analysis of the disassembly of self-immolative spacers based on cyclisation processes was performed. Five compounds were synthesized belonging to two different series, and their kinetic constants were determined. Electron-donating substituents gave a slight acceleration but the main effect was steric, and the Thorpe-Ingold effect was indeed particularly effective. Comparison with the self-immolative spacers based on elimination processes showed that cyclisations gave comparable or lower rate, but the corresponding spacers are more difficult to modulate.
基于环化过程对自毁型间隔基的拆解进行了动力学分析。合成了属于两个不同系列的五种化合物，并测定了它们的动力学常数。供电子取代基有轻微加速作用，但主要影响是空间位阻，索普-英戈尔德效应确实特别有效。与基于消除过程的自毁型间隔基相比，环化反应的速率相当或更低，但相应的间隔基更难调控。
