Ding Decai, Dong Haiyan, Wang Chuan
Hefei National Laboratory for Physical Science at the Microscale, Department of Chemistry, Center for Excellence in Molecular Synthesis, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China.
Hefei National Laboratory for Physical Science at the Microscale, Department of Chemistry, Center for Excellence in Molecular Synthesis, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China.
iScience. 2020 Apr 24;23(4):101017. doi: 10.1016/j.isci.2020.101017. Epub 2020 Apr 3.
Herein we demonstrate the successful application of reductive strategy in the asymmetric domino ring opening/cross-coupling reaction of prochiral cyclobutanones. Under the catalysis of a chiral nickel complex, various aryl iodide-tethered cyclobutanones were reacted with alkyl bromides as the electrophilic coupling partner, providing a variety of chiral indanones bearing a quaternary stereogenic center in highly enantioselective manner, which can be further converted to diverse benzene-fused cyclic compounds including indane, indene, dihydrocoumarin, and dihydroquinolinone. The preliminary mechanistic investigations support a mechanism involving Ni(I)-mediated enantiotopic C-C σ-bond activation of cyclobutanones as key elementary step in the catalytic cycle.
在此，我们展示了还原策略在手性环丁酮的不对称多米诺开环/交叉偶联反应中的成功应用。在手性镍配合物的催化下，各种芳基碘连接的环丁酮与作为亲电偶联伙伴的烷基溴反应，以高对映选择性的方式提供了多种带有季碳立体中心的手性茚满酮，这些手性茚满酮可进一步转化为多种稠苯环化合物，包括茚满、茚、二氢香豆素和二氢喹啉酮。初步的机理研究支持了一种机理，该机理涉及镍（I）介导的环丁酮对映异位C-C σ键活化，这是催化循环中的关键基元步骤。
