rume-bipam-catalyzed asymmetric addition of arylboronic acids to aliphatic aldehydes and α-ketoestersrume-bipam-catalyzed arylboronic酸脂族醛和α-ketoesters不对称加成反应.pdfVIP

Molecules 2011, 16, 5020-5034; doi:10.3390/molecule OPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Ru/Me-BIPAM-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes and α-Ketoesters Yasunori Yamamoto *, Tomohiko Shirai, Momoko Watanabe, Kazunori Kurihara and Norio Miyaura Division of Chemical Process Engineering, Graduate School of Engineering, Hokkaido University, kita 13, Nishi 8, Kita-ku, Sapporo 060-8628, Japan * Author to whom correspondence should be addressed; E-Mail: yasuyama@eng.hokudai.ac.jp; Tel.: +81-11-706-6560; Fax: +81-11-706-6560. Received: 31 May 2011 in revised form: 13 June 2011 / Accepted: 15 June 2011 / Published: 17 June 2011 Abstract: A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(aryl)methanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM) achieved excellent enantioselectivities. Keywords: asymmetric catalyst; bidentate phosphoramidite ligand; ruthenium catalyzed arylation 1. Introduction Transmetalation between organoboronic reagents and transition metals is a fundamental process involved in many metal-catalyzed C-C bond-forming reactions [1,2]. In this field, we reported a new catalytic cycle starting from transmetalation to give an organorhodium(I), -palladium(II) or -ruthenium(II) intermediate for 1,4-addition of org