Nanda Tanmayee, Biswal Pragati, Pati Bedadyuti Vedvyas, Banjare Shyam Kumar, Ravikumar Ponneri Chandrababu
National Institute of Science Education and Research (NISER), HBNI, Bhubaneswar 752050, India.
School of Chemical Sciences, National Institute of Science Education and Research (NISER), HBNI, Bhubaneswar 752050, India.
J Org Chem. 2021 Feb 5;86(3):2682-2695. doi: 10.1021/acs.joc.0c02700. Epub 2021 Jan 11.
Strain-driven palladium/-heterocyclic carbene-catalyzed C-C bond activation of diphenylcyclopropenone (DPC) has been explored for one-step access to trisubstituted α,β-unsaturated esters and amides. The designed transformation works under mild conditions providing exclusively a single stereoisomer. Mechanistic studies support the oxidative addition of the C-C bond of cyclopropenone to in-situ-generated Pd(0) intermediate. We have proved that vinylic hydrogen in the product is coming from phenol/aniline through deuterium-labeling studies. Late-stage functionalization of bioactive molecules such as procaine, estrone, and hymecromone demonstrates the robustness of this protocol.
已探索了应变驱动的钯/杂环卡宾催化的二苯基环丙烯酮（DPC）的C-C键活化反应，用于一步合成三取代的α,β-不饱和酯和酰胺。所设计的转化反应在温和条件下进行，仅生成单一立体异构体。机理研究支持环丙烯酮的C-C键向原位生成的Pd(0)中间体进行氧化加成。通过氘标记研究，我们已证明产物中的乙烯基氢来自苯酚/苯胺。生物活性分子如普鲁卡因、雌酮和羟甲香豆素的后期官能团化证明了该方法的实用性。
