文献类型：期刊文献

英文题名：Benzylic Functionalization of Anthrones via the Asymmetric Ring Opening of Oxabicycles Utilizing a Fourth-Generation Rhodium Catalytic System

作者：Loh, Charles C. J.[1];Fang, Xiang[1,2,3];Peters, Brendan[1];Lautens, Mark[1]

机构：[1]Univ Toronto, Dept Chem, Davenport Chem Labs, Toronto, ON M5S 3H6, Canada;[2]E China Univ Sci & Technol, Sch Chem & Mol Engn, Adv Mat Lab, Shanghai 200237, Peoples R China;[3]E China Univ Sci & Technol, Sch Chem & Mol Engn, Inst Fine Chem, Shanghai 200237, Peoples R China

年份：2015

卷号：21

期号：40

起止页码：13883

外文期刊名：CHEMISTRY-A EUROPEAN JOURNAL

收录：;EI(收录号：20153601236009);WOS:【SCI-EXPANDED(收录号:WOS:000363331200004)，CCR-EXPANDED(收录号:WOS:000363331200004)】；

基金：The authors thank Solvias AG, Umicore and Johnson Matthey for the generous donation of ligands and rhodium catalysts. The National Sciences and Engineering Research Council (NSERC), the University of Toronto and Alphora Inc. are gratefully acknowledged for financial support. C.C.J.L. thank the Deutsche Forschungsgemeinschaft (DFG) for a postdoctoral fellowship (LO 2065/1-1). F.X. thank the National Natural Science Foundation of China (Nos. 21172148, 21202044) and China Scholarship Council (Nos. 201306745008) for funding. B.P. thank NSERC for graduate funding. Dr. Alan Lough (University of Toronto) is gratefully acknowledged for single crystal X-ray analysis.

语种：英文

外文关键词：asymmetric catalysis; dearomatization; oxabicycles; rhodium; ring opening reactions

摘要：While anthrones exist as privileged scaffolds in bioactive molecules, the enantioselective functionalization of anthrones is surprisingly scarce in the literature, with no asymmetric transition metal catalyzed example to date. Herein, we report the first asymmetric transition metal catalyzed benzylic functionalization of anthrones through the rhodium(I) catalyzed desymmetrization of oxabicycles. As previously developed rhodium(I) systems were found to be unsuitable for this substrate, a new robust fourth-generation [Rh(cod)OH](2) based catalytic system was developed to address synthetic challenges in this protocol.