Fachbereich Chemie, Philipps-Universität Marburg , Hans-Meerwein-Strasse 4, 35043 Marburg, Germany.
School of Chemistry and Environmental Engineering, Jiangsu University of Technology , Changzhou 213001, PR China.
J Org Chem. 2017 Sep 1;82(17):8995-9005. doi: 10.1021/acs.joc.7b01394. Epub 2017 Aug 17.
The enantioselective catalytic alkynylation of aromatic aldehydes is reported using a sterically highly hindered bis-cyclometalated rhodium-based Lewis acid catalyst featuring the octahedral metal as the only stereogenic center. Yields of 58-98% with 79-98% enantiomeric excess were achieved using 1-2 mol % of catalyst. This work complements previous work from our laboratory on the enantioselective alkynylation of 2-trifluoroacetyl imidazoles (Chem. - Eur. J. 2016, 22, 11977-11981) and trifluoromethyl ketones (J. Am. Chem. Soc. 2017, 139, 4322-4325) using catalysts with octahedral metal-centered chirality.
报道了使用具有八面体金属作为唯一手性中心的位阻大的双环金属铑基路易斯酸催化剂，对芳香醛进行对映选择性催化炔基化反应。使用 1-2 摩尔%的催化剂，可获得 58-98%的收率和 79-98%的对映体过量。这项工作补充了我们实验室以前使用具有八面体金属中心手性的催化剂对 2-三氟乙酰基咪唑（Chem. - Eur. J. 2016, 22, 11977-11981）和三氟甲基酮（J. Am. Chem. Soc. 2017, 139, 4322-4325）进行对映选择性炔基化反应的工作。
