Wang Yidong, Zhang Peichao, Liu Yuan, Xia Fei, Zhang Junliang
Shanghai Key Laboratory of Green Chemistry and Chemical Processes , School of Chemistry and Molecular Engineering , East China Normal University , 3663 N. Zhongshan Road , Shanghai 200062 , China . Email:
State Key Laboratory of Organometallic Chemistry , Shanghai Institute of Organic Chemistry , CAS , 345 Lingling Road , Shanghai 200032 , China.
Chem Sci. 2015 Oct 1;6(10):5564-5570. doi: 10.1039/c5sc01827g. Epub 2015 Jun 23.
A highly enantioselective [2+2] a [4+2]-cycloaddition of 3-styrylindoles to -allenamides catalyzed by identical gold(i)/chiral phosphoramidite complexes is presented, which provides facile access to synthetically valuable, optically active substituted cyclobutanes and tetrahydrocarbazoles. The cycloaddition mode unexpectedly depends on the electronic nature of the -substituent 3-styrylindoles, the origin of which could be well rationalized using DFT calculations and experimental results. To the best of our knowledge, the present work represents the first example of such an impressive substituent effect in tuning the reaction mode with high chemo-, regio- and enantioselectivity in asymmetric gold catalysis.
报道了由相同的金（I）/手性亚磷酰胺配合物催化的3-苯乙烯基吲哚与α-烯丙基酰胺的高度对映选择性[2+2]和[4+2]环加成反应，该反应为合成有价值的光学活性取代环丁烷和四氢咔唑提供了便捷途径。环加成模式出乎意料地取决于3-苯乙烯基吲哚α-取代基的电子性质，利用密度泛函理论计算和实验结果可以很好地解释其起源。据我们所知，目前的工作代表了在不对称金催化中，这种令人印象深刻的取代基效应在以高化学、区域和对映选择性调节反应模式方面的首个实例。
