Organocatalytic Asymmetric Tandem Nazarov Cyclization/Semipinacol Rearrangement: Rapid Construction of Chiral Spiro[4.4]nonane-1,6-diones

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• 作者：Bin-Miao Yang ; Pei-Jun Cai ; Yong-Qiang Tu ; Zhi-Xiang Yu ; Zhi-Min Chen ; Shuang-Hu Wang ; Shao-Hua Wang ; Fu-Min Zhang
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：July 8, 2015
• 年：2015
• 卷：137
• 期：26
• 页码：8344-8347
• 全文大小：395K
• ISSN：1520-5126

文摘

A novel organocatalytic asymmetric tandem Nazarov cyclization/semipinacol rearrangement reaction using 鈥渦nactivated鈥?substrates has been developed, generating a series of chiral spiro[4.4]nonane-1,6-diones in up to 96% yield and 97% enantiomeric excess. Significantly, it is the first direct example for asymmetric synthesis of cyclopentanones with four stereocenters using Nazarov cyclization. DFT calculations have been applied to understand the reaction mechanism, stereochemistry, and substituent effects.