Coverdale James P C, Sanchez-Cano Carlos, Clarkson Guy J, Soni Rina, Wills Martin, Sadler Peter J
Department of Chemistry, University of Warwick, Coventry, CV4 7AL (UK).
Chemistry. 2015 May 26;21(22):8043-6. doi: 10.1002/chem.201500534. Epub 2015 Apr 8.
Asymmetric transfer hydrogenation (ATH) is an important process in organic synthesis for which the Noyori-type Ru(II) catalysts [(arene)Ru(Tsdiamine)] are now well established and widely used. We now demonstrate for the first time the catalytic activity of the osmium analogues. X-ray crystal structures of the 16-electron Os(II) catalysts are almost identical to those of Ru(II). Intriguingly the precursor complex was isolated as a dichlorido complex with a monodentate amine ligand. The Os(II) catalysts are readily synthesised (within 1 h) and exhibit excellent enantioselectivity in ATH reactions of ketones.
不对称转移氢化(ATH)是有机合成中的一个重要过程,诺伊里型钌(II)催化剂[(芳烃)Ru(二胺)]现已得到广泛认可并被广泛应用。我们首次证明了锇类似物的催化活性。16电子锇(II)催化剂的X射线晶体结构与钌(II)的几乎相同。有趣的是,前体配合物以带有单齿胺配体的二氯配合物形式被分离出来。锇(II)催化剂易于合成(1小时内),并且在酮的ATH反应中表现出优异的对映选择性。