Bae Song, Zhang Changhe, Gillard Rachel M, Lupton David W
School of Chemistry, Monash University, Clayton, 3800, Victoria, Australia.
Angew Chem Int Ed Engl. 2019 Sep 16;58(38):13370-13374. doi: 10.1002/anie.201907111. Epub 2019 Aug 13.
While the enantioselective Rauhut-Currier reaction is established with bis(enone) substrates, it is yet to be reported with less electrophilic bis(enoate) substrates. By exploiting high-nucleophilicity N-heterocyclic carbenes, it is possible to achieve Rauhut-Currier reactions with these substrates. The reaction is demonstrated with a range of intramolecular reactions (20 examples) and six esterification/RC reaction cascades, which all proceed with high enantioselectivity (most >93:7 er).
虽然对映选择性劳乌特-库里尔反应已在双烯酮底物中得到确立，但对于亲电性较低的双烯酸酯底物，尚未见有相关报道。通过利用高亲核性的氮杂环卡宾，可实现这些底物的劳乌特-库里尔反应。该反应通过一系列分子内反应（20个实例）和六个酯化/RC反应级联得以证明，所有这些反应均以高对映选择性进行（大多数对映体过量>93:7）。
