Wassenaar Jeroen, Detz Remko J, de Boer Sandra Y, Lutz Martin, van Maarseveen Jan H, Hiemstra Henk, Reek Joost N H
§Crystal and Structural Chemistry, Bijvoet Center for Biomolecular Research, Faculty of Science, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.
‡Biomolecular Synthesis, van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands.
J Org Chem. 2015 Apr 3;80(7):3634-42. doi: 10.1021/acs.joc.5b00438. Epub 2015 Mar 16.
A small library of highly tunable chiral Clickphine P,N-ligands has been prepared in an enantioselective fashion by Cu(I)-catalyzed asymmetric propargylic amination using a single chiral complex and a subsequent in situ cycloaddition click reaction. The scope of the propargylic amination to yield optically active triazolyl amines is described. The amines are transformed in a one-pot procedure to the corresponding Ir-Clickphine complexes, which serve as catalysts for the asymmetric hydrogenation of di-, tri-, and tetrasubstituted unfunctionalized alkenes. Enantioselectivities of up to 90% ee were obtained in these hydrogenations, which are among the best reported in the case of the tetrasubstituted substrate 2-(4'-methoxyphenyl)-3-methylbut-2-ene (9) (87% ee). This is a demonstration of the effective use of the chiral pool, as from one chiral catalyst a library of chiral Ir complexes has been synthesized that can hydrogenate various alkenes with high selectivity.
通过使用单一手性配合物的铜（I）催化不对称炔丙基胺化反应以及随后的原位环加成点击反应，以对映选择性方式制备了一个小型的可高度调节的手性Clickphine P，N配体库。描述了炔丙基胺化反应生成光学活性三唑基胺的范围。胺通过一锅法转化为相应的铱-Clickphine配合物，这些配合物用作二取代、三取代和四取代未官能化烯烃不对称氢化反应的催化剂。在这些氢化反应中获得了高达90% ee的对映选择性，这在四取代底物2-（4'-甲氧基苯基）-3-甲基丁-2-烯（9）（87% ee）的情况下是报道的最佳结果之一。这证明了手性库的有效利用，因为从一种手性催化剂合成了一个手性铱配合物库，该库可以高选择性地氢化各种烯烃。
