Sanz-Marco Amparo, Blay Gonzalo, Muñoz M Carmen, Pedro José R
Department de Química Orgànica-Facultat de Química, Universitat de València, C/Dr. Moliner 50, 46100, Burjasso, Spain.
Departament de Física Aplicada, Universitat Politècnica de València, Camí de Vera s/n, 46022, València, Spain.
Chemistry. 2016 Jul 11;22(29):10057-64. doi: 10.1002/chem.201601303. Epub 2016 Jun 23.
The first catalytic enantioselective conjugate alkynylation of α,β-unsaturated 1,1,1-trifluoromethyl ketones has been carried out. Terminal alkynes and 1,3-diynes were treated with trifluoromethyl ketones in the presence of a low catalytic load of a Cu(I) -MeOBIPHEP complex (2.5 mol %) and triethylamine (10 mol %) to give the corresponding trifluoromethyl ketones bearing a propargylic stereogenic center at the β position with good yields and excellent enantiomeric excesses in most of the cases. No 1,2-addition products were formed under the reaction conditions. The procedure showed broad substrate scope for alkyne, diyne, and enone. A rationale for the observed stereochemistry has been provided. Finally, the potential application of the reaction products in the synthesis of chiral tetrahydrofurans bearing a trifluoromethylated quaternary stereocenter has been devised.
已实现首例α,β-不饱和1,1,1-三氟甲基酮的催化对映选择性共轭炔基化反应。在低催化量的Cu(I)-MeOBIPHEP配合物（2.5 mol%）和三乙胺（10 mol%）存在下，端炔和1,3-二炔与三氟甲基酮反应，在大多数情况下，能以良好的产率和优异的对映体过量得到在β位带有炔丙基手性中心的相应三氟甲基酮。在该反应条件下未形成1,2-加成产物。该方法对炔烃、二炔和烯酮显示出广泛的底物范围。已对观察到的立体化学给出了一种解释。最后，设计了该反应产物在合成带有三氟甲基化季碳手性中心的手性四氢呋喃中的潜在应用。
