Huang Yong, Song Liangliang, Gong Lei, Meggers Eric
Key Laboratory for Chemical Biology of Fujian Province and Department of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, 361005, Xiamen, People's Republic of China.
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany.
Chem Asian J. 2015 Dec;10(12):2738-43. doi: 10.1002/asia.201500764. Epub 2015 Sep 7.
A bis-cyclometalated chiral-at-metal rhodium complex catalyzes the Diels-Alder reaction between N-Boc-protected 3-vinylindoles (Boc = tert-butyloxycarbonyl) and β-carboxylic ester-substituted α,β-unsaturated 2-acyl imidazoles with good-to-excellent regioselectivity (up to 99:1) and excellent diastereoselectivity (>50:1 d.r.) as well as enantioselectivity (92-99% ee) under optimized conditions. The rhodium catalyst serves as a chiral Lewis acid to activate the 2-acyl imidazole dienophile by two-point binding and overrules the preferred regioselectivity of the uncatalyzed reaction.
一种双环金属化的金属手性铑配合物催化N - 叔丁氧羰基保护的3 - 乙烯基吲哚（Boc = 叔丁氧羰基）与β - 羧酸酯取代的α,β - 不饱和2 - 酰基咪唑之间的狄尔斯 - 阿尔德反应，在优化条件下具有良好至优异的区域选择性（高达99:1）、出色的非对映选择性（>50:1 d.r.）以及对映选择性（92 - 99% ee）。铑催化剂作为手性路易斯酸，通过两点结合活化2 - 酰基咪唑亲双烯体，并改变了未催化反应的首选区域选择性。
