Department of Chemistry & Medicinal Chemistry Program, Life Sciences Institute, National University of Singapore 3, Science Drive 3, Singapore 117543 (Singapore).
Angew Chem Int Ed Engl. 2014 Mar 10;53(11):2964-8. doi: 10.1002/anie.201307757. Epub 2014 Feb 12.
The first phosphine-catalyzed enantioselective γ-addition with prochiral nucleophiles and 2,3-butadienoates as the reaction partners has been developed. Both 3-alkyl- and 3-aryl-substituted oxindoles could be employed in this process, which is catalyzed by a chiral phosphine that is derived from an amino acid, thus affording oxindoles that bear an all-carbon quaternary center at the 3-position in high yields and excellent enantioselectivity. The synthetic value of these γ-addition products was demonstrated by the formal total synthesis of two natural products and by the preparation of biologically relevant molecules and structural scaffolds.
首次发展了手性膦催化的前手性亲核试剂与 2,3-丁二烯酸酯的对映选择性 γ-加成反应。该反应可以使用 3-烷基和 3-芳基取代的氧化吲哚作为反应底物，由氨基酸衍生的手性膦催化，以高产率和优异的对映选择性得到在 3-位具有全碳季碳中心的氧化吲哚产物。这些 γ-加成产物的合成价值通过两个天然产物的形式全合成以及生物相关分子和结构骨架的制备得到了证明。
