Polishchuk Iuliia, Sklyaruk Jan, Lebedev Yury, Rueping Magnus
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, Aachen, Germany.
KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia.
Chemistry. 2021 Apr 1;27(19):5919-5922. doi: 10.1002/chem.202005508. Epub 2021 Mar 3.
Half-sandwich iridium complexes bearing bidentate urea-phosphorus ligands were found to catalyze the direct reductive amination of aromatic and aliphatic ketones under mild conditions at 0.5 mol % loading with high selectivity towards primary amines. One of the complexes was found to be active in both the Leuckart-Wallach (NH CO H) type reaction as well as in the hydrogenative (H /NH AcO) reductive amination. The protocol with ammonium formate does not require an inert atmosphere, dry solvents, as well as additives and in contrast to previous reports takes place in hexafluoroisopropanol (HFIP) instead of methanol. Applying NH CO D or D resulted in a high degree of deuterium incorporation into the primary amine α-position.
发现带有双齿脲磷配体的半三明治铱配合物在温和条件下以0.5 mol%的负载量催化芳香族和脂肪族酮的直接还原胺化反应，对伯胺具有高选择性。其中一种配合物在Leuckart-Wallach（NH CO H）型反应以及氢化（H /NH AcO）还原胺化反应中均具有活性。使用甲酸铵的方案不需要惰性气氛、干燥溶剂以及添加剂，并且与先前的报道相反，该反应在六氟异丙醇（HFIP）中而非甲醇中进行。使用NH CO D或D会导致大量氘掺入伯胺的α位。
