Arynes are straightforward and effective synthons for p-extension accompanying by vicinal difunction-alization simultaneously,thereby being ideal building blocks for polycyclic aromatic hydrocarbons(PAHs)construction....Arynes are straightforward and effective synthons for p-extension accompanying by vicinal difunction-alization simultaneously,thereby being ideal building blocks for polycyclic aromatic hydrocarbons(PAHs)construction.However,C=C triple bond in an aromatic system,with the distorted bond angle and shortened bond distance,arouses tremendous challenges for thermodynamic stability and kinetically reactive selectivity,especially for heteroarynes.Herein,controllable aryne generation was achieved for nitrogen-doped polycyclic aromatic hydrocarbons via designed cyclic pyridine-benzene λ^(3)-iodanes,in which the iodine ensured the thermodynamic stability and kinetic site-selectivity via p→π*interaction with aryne for chemo-and regio-selectivity.The“pyridyne-benzyne”model enabled the preeminent ortho-selectivity with nucleophilic capture and consecutive[4+2]-cycloaddition for π conjugation exten-sion,not only assembling for N-doped PAHs with adjustable Twisted Intramolecular Charge Transfer(TICT)and inverse Suppression of Proximity Effect(SOPE)phenomenon but also establishing a reliable empirical formula for regulating generation and release of arynes.展开更多
基金supported by the National Natural Science Foun-dation of China(22125103 and 22401095)the Shanghai Munic-ipal Major Basic Research Project(22JC1401000)+2 种基金the Shanghai Rising-Star Program(24QB2704700)the National Key R&D Pro-gram of China(2022YFA1505100 and 2023YFA1508600)the China Postdoctoral Science Foundation(BX20230127)。
文摘Arynes are straightforward and effective synthons for p-extension accompanying by vicinal difunction-alization simultaneously,thereby being ideal building blocks for polycyclic aromatic hydrocarbons(PAHs)construction.However,C=C triple bond in an aromatic system,with the distorted bond angle and shortened bond distance,arouses tremendous challenges for thermodynamic stability and kinetically reactive selectivity,especially for heteroarynes.Herein,controllable aryne generation was achieved for nitrogen-doped polycyclic aromatic hydrocarbons via designed cyclic pyridine-benzene λ^(3)-iodanes,in which the iodine ensured the thermodynamic stability and kinetic site-selectivity via p→π*interaction with aryne for chemo-and regio-selectivity.The“pyridyne-benzyne”model enabled the preeminent ortho-selectivity with nucleophilic capture and consecutive[4+2]-cycloaddition for π conjugation exten-sion,not only assembling for N-doped PAHs with adjustable Twisted Intramolecular Charge Transfer(TICT)and inverse Suppression of Proximity Effect(SOPE)phenomenon but also establishing a reliable empirical formula for regulating generation and release of arynes.
