title: A Chiral Nitrogen Ligand for Enantioselective, Iridium-Catalyzed Silylation of Aromatic C-H Bonds.
abstract: Iridium catalysts containing dative nitrogen ligands are highly active for the borylation and silylation of C-H bonds, but chiral analogs of these catalysts for enantioselective silylation reactions have not been developed. We report a new chiral pyridinyloxazoline ligand for enantioselective, intramolecular silylation of symmetrical diarylmethoxy diethylsilanes. Regioselective and enantioselective silylation of unsymmetrical substrates was also achieved in the presence of this newly developed system. Preliminary mechanistic studies imply that C-H bond cleavage is irreversible, but not the rate-determining step.
authors.affiliation: Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry and Molecular Engineering, Peking University, Beijing, China.|Department of Chemistry, University of California, Berkeley, CA, 94720, USA.
authors.forename: Bo
authors.initials: B
authors.lastname: Su
authors.affiliation: Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry and Molecular Engineering, Peking University, Beijing, China.
authors.forename: Tai-Gang
authors.initials: TG
authors.lastname: Zhou
authors.affiliation: Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry and Molecular Engineering, Peking University, Beijing, China.
authors.forename: Xian-Wei
authors.initials: XW
authors.lastname: Li
authors.affiliation: Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry and Molecular Engineering, Peking University, Beijing, China.
authors.forename: Xiao-Ru
authors.initials: XR
authors.lastname: Shao
authors.affiliation: Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry and Molecular Engineering, Peking University, Beijing, China.
authors.forename: Pei-Lin
authors.initials: PL
authors.lastname: Xu
authors.affiliation: Merck Research Laboratories, 2015 Galloping Hill Road, Kenilworth, NJ, 07033, USA.
authors.forename: Wen-Lian
authors.initials: WL
authors.lastname: Wu
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA, 94720, USA.
authors.forename: John F
authors.initials: JF
authors.lastname: Hartwig
authors.affiliation: Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry and Molecular Engineering, Peking University, Beijing, China.|State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, China.
authors.forename: Zhang-Jie
authors.initials: ZJ
authors.lastname: Shi
mesh_terms: D002384:Catalysis; D007495:Iridium / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry*; D010080:Oxazoles / Q000737:chemistry*; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D008024:Ligands; D010080:Oxazoles; D012821:Silanes; D007495:Iridium; D009584:Nitrogen
keywords: C−H activation; asymmetric catalysis; chiral N,N ligand; iridium; silylation