Asymmetric Synthesis of Chiral Cyclopentanes Bearing an All‐Carbon Quaternary Stereocenter by Zirconium‐Catalyzed Double Carboalumination

• Published in: Angewandte Chemie International Edition 2017-09, Vol.56 (38), p.11502-11505
• Main Authors: Xu, Shiqing, Wang, Chuan, Komiyama, Masato, Tomonari, Yasuhiko, Negishi, Ei‐ichi
• Format: Article
• Language: English
• Subjects: Asymmetric synthesis; carbometalation; Chemical synthesis; cyclopentanes; Dienes; Enantiomers; quaternary stereocenters; Zirconium
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201706198

Herein, we report a zirconium‐catalyzed enantio‐ and diastereoselective inter/intramolecular double carboalumination of unactivated 2‐substituted 1,5‐dienes, which provides efficient and direct access to chiral cyclopentanes through the generation of two stereocenters, including one all‐carbon quaternary stereocenter, generally with excellent diastereo‐ and high enantioselectivity. This tandem carboalumination process creates two new C−C bonds as well as one C−Al bond, which can be oxidized in situ with O2 or hydrolyzed. Furthermore, the obtained chiral cyclopentanes can be readily functionalized to provide various chiral compounds. All‐carbon quaternary stereocenters: A zirconium‐catalyzed double carboalumination of various unactivated 1,5‐dienes provides efficient access to chiral cyclopentanes with two stereocenters, including one all‐carbon quaternary stereocenter, through the formation of two new C−C bonds as well as one C−Al bond with high diastereo‐ and enantioselectivity.