Asymmetric Synthesis of Rauhut–Currier type Products by a Regioselective Mukaiyama Reaction under Bifunctional Catalysis

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• 作者：María Frias ; Rubén Mas-Ballesté ; Saira Arias ; Cuauhtemoc Alvarado ; José Alemán
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：January 18, 2017
• 年：2017
• 卷：139
• 期：2
• 页码：672-679
• 全文大小：637K
• ISSN：1520-5126

文摘

The reactivity and the regioselective functionalization of silyl–diene enol ethers under a bifunctional organocatalyst provokes a dramatic change in the regioselectivity, from the 1,5- to the 1,3-functionalization. This variation makes possible the 1,3-addition of silyl–dienol ethers to nitroalkenes, giving access to the synthesis of tri- and tetrasubstituted double bonds in Rauhut–Currier type products. The process takes place under smooth conditions, nonanionic conditions, and with a high enantiomeric excess. A rational mechanistic pathway is presented based on DFT and mechanistic experiments.