文献类型：期刊文献

英文题名：Post-Functionalization of Supramolecular Polymers on Surface and the Chiral Assembly-Induced Enantioselective Reaction

作者：Li, Deng-Yuan[1,2];Zhu, Ya-Cheng[1,2];Li, Shi-Wen[1,2];Shu, Chen-Hui[1,2];Liu, Pei-Nian[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Frontiers Sci Ctr Materiobiol & Dynam Chem, Key Lab Adv Mat,State Key Lab Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Chem Engn, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Feringa Nobel Prize Scientist, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2021

卷号：60

期号：20

起止页码：11370

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20211510189167);WOS:【SCI-EXPANDED(收录号:WOS:000637437300001)】；

基金：This work was supported by the National Natural Science Foundation of China (Nos. 21925201 and 91845110), Shanghai Municipal Science and Technology Major Project (Grant No. 2018SHZDZX03), Natural Science Foundation of Shanghai (20ZR1414200), the Programme of Introducing Talents of Discipline to Universities (B16017), Program of the Shanghai Committee of Sci. & Tech. (Project No. 18520760700) and the Program for Eastern Scholar Distinguished Professor. We thank the Research Center of Analysis and Test of East China University of Science and Technology for help in the characterization.

语种：英文

外文关键词：enantioselective reaction; on-surface reactions; post-functionalization; scanning tunneling microscopy; supramolecular polymers

摘要：Although post-functionalization is extensively used to introduce diverse functional groups into supramolecular polymers (SPs) in solution, post-functionalization of SPs on surfaces still remains unexplored. Here we achieved the on-surface post-functionalization of two SPs derived from 5,10,15-tri-(4-pyridyl)-20-bromophenyl porphyrin (Br-TPyP) via cross-coupling reactions on Au(111). The ladder-shaped, Cu-coordinated SPs preformed from Br-TPyP were functionalized through Heck reaction with 4-vinyl-1,1 '-biphenyl. In the absence of Cu, Br-TPyP formed chiral SPs as two enantiomers via self-assembly, which were functionalized via divergent cross-coupling reaction with 4-isocyano-1,1 '-biphenyl (ICBP). Surprisingly, this reaction was discovered as an enantioselective on-surface reaction induced by the chirality of SPs. Mechanistic analysis and DFT calculations indicated that after debromination of Br-TPyP and the first addition of ICBP, only one attack direction of ICBP to the chiral SP intermediate is permissive in the second addition step due to the steric hindrance, which guaranteed the high enantioselectivity of the reaction.