文献类型：期刊文献

英文题名：Adjustable Regioselectivity for the Diels-Alder Reactions of Sulfolenodipyrrins upon Molecular Engineering on H-Bonds

作者：Liu, Jiayang[1];Zhang, Yiqi[1];Fan, Peijun[1];Feng, Yuci[2];Duan, Tingting[3];Zhou, Ying[1];Zheng, Shaoyu[1];Li, Qizhao[1];Li, Yuxin[4];Liu, Xiujun[1];Wu, Xin-Yan[1];Li, Chengjie[1]

机构：[1]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Shanghai Key Lab Funct Mat Chem, Sch Chem & Mol Engn,Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem Engn, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Int Elite Engn Sch, Shanghai 200237, Peoples R China;[4]Heilongjiang Univ, Sch Chem & Mat Sci, Key Lab Funct Inorgan Mat Chem MOE, Harbin 150080, Peoples R China

年份：2024

卷号：89

期号：21

起止页码：15678

外文期刊名：JOURNAL OF ORGANIC CHEMISTRY

收录：;EI(收录号：20244317232575);WOS:【SCI-EXPANDED(收录号:WOS:001335282400001)】；

基金：This work was financially supported by the National Natural Science Foundation of China (22075077, 22131005, 22201074, and 22108078), the Natural Science Foundation of Shanghai (23ZR1415600, 22ZR1416100), the Shanghai Rising-Star Program (23QA1402100), and the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Addition reactions - Atomic emission spectroscopy - Hydrogen bonds - Red Shift - Regioselectivity

摘要：The Diels-Alder reactions of sulfolenodipyrrins prove to be an efficient way to construct aromatic ring-fused dipyrrins. However, adjustable annulation is still hard to achieve. To address this, molecular engineering on the H-bond has been employed. The alpha-position aryl group-modified sulfolenodipyrrins have been synthesized to react with various dienophiles in Diels-Alder reactions, affording the monoannulation products with different regioselectivity in good yields (45-76%). The remaining sulfolenopyrrole in monoadducts can undergo further fusion in the presence of dienophiles and TEMPO, giving the bisadducts with a lactam subunit in an appropriate yield. According to the crystal structures and theoretical calculations, the intramolecular H-bonds between the alpha-substituent and the nearby pyrrole confine the conjugation pathway of the dipyrrin core. With respect to the normal NH-sulfolenopyrrole, the imino-type one features low aromaticity, from which SO2 extrusion generates more stable dipyrrin-diene, achieving regioselectivity. In addition, aromatic ring fusion results in red-shifted absorption and emission spectra, and the annulation units regulate the emission intensity. This work shows the versatility of intramolecular H-bonds in regulating the reaction through confinement of the conjugation system.