Huang Bo-Wei, Han Jeng-Liang
Department of Chemistry, National Chung Hsing University, Taichung City 40227 Taiwan, R.O.C.
J Org Chem. 2023 Dec 1;88(23):16376-16390. doi: 10.1021/acs.joc.3c01885. Epub 2023 Nov 10.
A vinylogous addition reaction of allyl aryl ketones with good yields and excellent regioselectivity catalyzed by squaramide catalysts has been developed. A series of chiral tertiary alcohols and bicyclic pyrrolidones could be synthesized in good to excellent yields, enantioselectivities, and diaseteroselectivities. Both experimental results and DFT calculations indicate that 1,2-addition reaction is favorable when the reaction is employed at a lower temperature, while the 1,4-addition/cyclization pathway is favorable when the reaction is employed at a higher temperature. Furthermore, the formation of compound can potentially arise from either the 1,4-addition/cyclization pathway or retro-aldol reaction of compound , followed by subsequent 1,4-addition/cyclization.
已开发出一种由方酰胺催化剂催化的烯丙基芳基酮的乙烯基类似加成反应，该反应产率高且区域选择性优异。一系列手性叔醇和双环吡咯烷酮能够以良好至优异的产率、对映选择性和非对映选择性合成。实验结果和密度泛函理论计算均表明，该反应在较低温度下进行时有利于1,2-加成反应，而在较高温度下进行时1,4-加成/环化途径更有利。此外，化合物 的形成可能源于1,4-加成/环化途径，也可能源于化合物 的逆羟醛反应，随后进行1,4-加成/环化。
