Rhodium‐Catalyzed Enantioselective Intramolecular CH Silylation for the Syntheses of Planar‐Chiral Metallocene Siloles1. (23rd April 2015)

• Record Type: Journal Article
• Authors: Zhang, Qing‐Wei; An, Kun; Liu, Li‐Chuan; Yue, Yuan; He, Wei
• Is Part Of: Angewandte Chemie. Volume 127:Number 23(2015)
• Page Start: 7022
• Page End: 7025
• Publication Date: 2015-04-23
• Subjects: Chiralität -- Ligandeneffekte -- Metallocene -- Rhodium -- Silicium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201502548
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Reported herein is the rhodium‐catalyzed enantioselective CH bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of ( S )‐TMS‐Segphos, the reactions took place under very mild conditions to afford metallocene‐fused siloles in good to excellent yields and with ee values of up to 97 %. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric CH silylations.