Department of Chemistry, The University of Kansas, Lawrence, Kansas 66045, USA.
Org Lett. 2010 Jul 2;12(13):3042-5. doi: 10.1021/ol101042x.
A stereochemical test has been used to probe the mechanism of decarboxylative allylation. This probe suggests that the mechanism of DcA reactions can change based on the substitution pattern at the alpha-carbon of the nucleophile; however, reaction via stabilized malonate nucleophiles is the lower energy pathway. Lastly, this mechanistic proposal has predictive power and can be used to explain chemoselectivities in decarboxylative reactions that were previously confounding.
立体化学测试已被用于探究脱羧烯丙基化反应的机理。该探针表明，脱羧烯丙基化反应的机理可以根据亲核体α-碳上的取代模式发生变化；然而，通过稳定的丙二酸酯亲核试剂进行的反应是能量较低的途径。最后，该机理假设具有预测能力，并可用于解释以前令人困惑的脱羧反应中的化学选择性。
