Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.
The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki-shi, Osaka 567-0047, Japan.
Org Lett. 2023 Feb 17;25(6):1040-1044. doi: 10.1021/acs.orglett.3c00259. Epub 2023 Feb 7.
The first enantioselective reaction of α-isocyanoacetonitriles was developed. The reaction of various α-isocyanoacetonitriles with ketimines using cinchona alkaloid amide-Cu(II) catalysts afforded imidazolines with consecutive tetrasubstituted stereogenic carbon centers in good yields and high diastereo- and enantioselectivities. The stereoselectivity of the reaction is explained on the basis of the control experiment and density functional theory (DFT) calculations. The products were subsequently converted into chiral compounds. This process highlights the possible use of α-isocyanoacetonitriles for asymmetric and organic syntheses.
首次发展了 α-异氰基乙腈的对映选择性反应。使用金鸡纳生物碱酰胺-Cu(II)催化剂，各种α-异氰基乙腈与亚胺反应，以高收率和高非对映选择性和对映选择性得到具有连续四个立体中心的咪唑啉。根据控制实验和密度泛函理论（DFT）计算，解释了反应的立体选择性。随后将产物转化为手性化合物。该过程突出了α-异氰基乙腈在不对称和有机合成中的可能用途。
