title: Rhodium-catalyzed enantioselective intramolecular C-H silylation for the syntheses of planar-chiral metallocene siloles.
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.
authors.affiliation: School of Medicine and Tsinghua-Peking Joint Centers for Life Science, Tsinghua University, Beijing 100084 (China).
authors.forename: Qing-Wei
authors.initials: QW
authors.lastname: Zhang
authors.affiliation: School of Medicine and Tsinghua-Peking Joint Centers for Life Science, Tsinghua University, Beijing 100084 (China).
authors.forename: Kun
authors.initials: K
authors.lastname: An
authors.affiliation: School of Medicine and Tsinghua-Peking Joint Centers for Life Science, Tsinghua University, Beijing 100084 (China).
authors.forename: Li-Chuan
authors.initials: LC
authors.lastname: Liu
authors.affiliation: School of Medicine and Tsinghua-Peking Joint Centers for Life Science, Tsinghua University, Beijing 100084 (China).
authors.forename: Yuan
authors.initials: Y
authors.lastname: Yue
authors.affiliation: School of Medicine and Tsinghua-Peking Joint Centers for Life Science, Tsinghua University, Beijing 100084 (China). whe@mail.tsinghua.edu.cn.
authors.forename: Wei
authors.initials: W
authors.lastname: He
mesh_terms: D002384:Catalysis; D005290:Ferric Compounds / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D005290:Ferric Compounds; D009942:Organometallic Compounds; D012821:Silanes; C540376:silole; D012238:Rhodium
keywords: chirality; ligand effects; metallocenes; rhodium; silicon