Remote Ester Groups Switch Selectivity: Diastereodivergent Synthesis of Tetracyclic Spiroindolines

详细信息    查看全文

• 作者：Jun Zhu ; Yong Liang ; Lijia Wang ; Zhong-Bo Zheng ; K. N. Houk ; Yong Tang
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：May 14, 2014
• 年：2014
• 卷：136
• 期：19
• 页码：6900-6903
• 全文大小：299K
• 年卷期：v.136,no.19(May 14, 2014)
• ISSN：1520-5126

文摘

Stereocontrol in the synthesis of structurally complex molecules, especially those with all-carbon quaternary stereocenters, remains a challenge. Here, we reported the preparation of a class of tetracyclic cyclopenta-fused spiroindoline skeletons through Cu(II)-catalyzed intramolecular [3 + 2] annulation reactions of donor鈥揳cceptor cyclopropanes with indoles. Both cis- and trans-diastereomers of tetracyclic spiroindolines are accessed with high selectivities by altering the remote ester groups of cyclopropanes. The origins of this stereocontrol are identified using DFT calculations: attractive interactions between the ester group and arene favor the generation of the trans isomer, while the formation of the cis isomer is preferred when steric repulsions become predominant.