Aggregation-Enabled Intermolecular Photo[2+2]cycloaddition of Aryl Terminal Olefins by Visible-Light Catalysis  

作　　者：Zan Liu Chao Zhou Tao Lei Xiao-Lei Nan Bin Chen Chen-Ho Tung Li-Zhu Wu 

机构地区：[1]Key Laboratory of Photochemical Conversion and Optoelectronic Materials,Technical Institute of Physics and Chemistry,The Chinese Academy of Sciences,Beijing 100190(China) [2]School of Future Technology,University of Chinese Academy of Sciences,Beijing 100049(China)

出　　处：《CCS Chemistry》2020年第1期582-588,共7页中国化学会会刊（英文）

基　　金：This work was supported financially by the Ministry of Science and Technology of China(2017YFA0206903);the National Natural Science Foundation of China(21861132004);the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17000000);the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(QYZDY-SSW-JSC029),and K.C.Wong Education Foundation.

摘　　要：Photo[2+2]cycloaddition of olefins is a sought-after tool for making cyclobutanes,which are the building blocks for a wide range of biologically active molecules and natural products.However,the formation of cyclobutane derivatives from aryl terminal olefins is problematic due to their high redox potential,and high energy in the excited state,making visible-light-absorbing photocatalyst difficult to realize either electron or energy transfer to olefins during the photocyclic addition process.Herein,we report,for the first time,the aggregationinduced photo[2+2]cycloaddition of two olefins by visible-light catalysis in homogeneous solution.An array of control experiments and spectroscopic analyses reveal that the terminal olefins tend to aggregate to form excimers/exciplexes,which possess much lower energy than their monomeric forms,and enables triplet energy transfer from excited Ir(ppy)3*to supramolecular self-assembly feasible,leading to homo and cross[2+2]photodimerization of the olefins to fabricate cyclobutanes at ambient conditions in good to excellent yields.

关 键 词：AGGREGATION aryl terminal olefin CYCLOBUTANE photocatalysis energy transfer 

分 类 号：O62[理学—有机化学]