Phosphinoylazidation of alkenes is a direct method to build nitrogen-and phosphorus-containing compounds from feed-stock chemicals.Notwithstanding the advances in other phosphinyl radical related difunctionalization o...Phosphinoylazidation of alkenes is a direct method to build nitrogen-and phosphorus-containing compounds from feed-stock chemicals.Notwithstanding the advances in other phosphinyl radical related difunctionalization of alkenes,catalytic phosphinoylazidation of alkenes has not yet been reported.Here,we describe the first iron-catalyzed intermolecular phosphinoylazidation of styrenes and unactivated alkenes.The method is practically useful and requires a relatively low loading of catalyst.Mechanistic studies confirmed the radical nature of the reaction and disclosed the unusually low activation energy 4.8 kcal/mol of radical azido group transfer from the azidyl iron(III)phthalocyanine species(PcFeulN3)to a benzylic radical.This work may help to clarify the mechanism of iron-catalyzed azidation,inspire other mechanism studies and spur further synthetic applications.展开更多
Four coordination polymers based on two bis-pyridyl-bis-amide ligands and three aromatic dicarboxylates with different substituent groups, namely, [Co（3-bpcb）x.5（NPH）（H20）]＂ 4H20 （1）, [Co（3-bpcb）（NIPH）] ...Four coordination polymers based on two bis-pyridyl-bis-amide ligands and three aromatic dicarboxylates with different substituent groups, namely, [Co（3-bpcb）x.5（NPH）（H20）]＂ 4H20 （1）, [Co（3-bpcb）（NIPH）] （2）, [Co（3-bpcb）0.5（5-H2AIP）]＂ 2H20 （3）, [Co（3-bpcd）0.5（5-H2AIP）（H20）]＂ 2H20 （4） [3-bpcb = N,N＇-bis（3-pyridinecarboxamide）-l,4-benzene, 3-bpcd = N,N＇-bis（3- pyridine）cyclohexane-l,4-dicarboxamide, H2NPH = 3-nitrophthalic acid, H2NIPH = 5-nitroisophthalic acid, 5-HaAIP = 5-aminoisophthalic acid] have been synthetized under hydrothermal conditions. Complex 1 displays a one dimensional （1D） chain based on the binuclear [Co2（NPH）2] units and 3-bpeb ligands, which is extended into a three dimensional （3D） supra- molecular framework through hydrogen bonding and n-n stacking interactions. In complex 2, the （3,5）-connected two dimen- sional （2D） layers are constructed from 1D Co-NIPH chains and bidentate-bridging 3-bpeb ligands. Complex 3 is a 2D double layer based on Co-5-H2AIP 2D layers and 3-bpeb pillars. Complex 4 also displays a 2D network, which is constructed from the Co-5-H2AIP 1D double chains and 3-bpcd ligands. Finally, complexes 2--4 are extended into 3D supramolecular frame- works by hydrogen bonding or n-re stacking interactions. The substituent groups of dicarboxylates play an important role in the assembly and structures of the title complexes. In addition, the fluorescent properties of complexes 1-4 and the electrochemi- cal behaviors of 3 and 4 at room temperature have been investigated.展开更多
文摘Phosphinoylazidation of alkenes is a direct method to build nitrogen-and phosphorus-containing compounds from feed-stock chemicals.Notwithstanding the advances in other phosphinyl radical related difunctionalization of alkenes,catalytic phosphinoylazidation of alkenes has not yet been reported.Here,we describe the first iron-catalyzed intermolecular phosphinoylazidation of styrenes and unactivated alkenes.The method is practically useful and requires a relatively low loading of catalyst.Mechanistic studies confirmed the radical nature of the reaction and disclosed the unusually low activation energy 4.8 kcal/mol of radical azido group transfer from the azidyl iron(III)phthalocyanine species(PcFeulN3)to a benzylic radical.This work may help to clarify the mechanism of iron-catalyzed azidation,inspire other mechanism studies and spur further synthetic applications.
基金supported by the Program for New Century Excellent Talents in University (NCET-09-0853)the National Natural Science Foundation of China (20871022, 21171025)the Natural Science Foundation of Liaoning Province (201102003)
文摘Four coordination polymers based on two bis-pyridyl-bis-amide ligands and three aromatic dicarboxylates with different substituent groups, namely, [Co（3-bpcb）x.5（NPH）（H20）]＂ 4H20 （1）, [Co（3-bpcb）（NIPH）] （2）, [Co（3-bpcb）0.5（5-H2AIP）]＂ 2H20 （3）, [Co（3-bpcd）0.5（5-H2AIP）（H20）]＂ 2H20 （4） [3-bpcb = N,N＇-bis（3-pyridinecarboxamide）-l,4-benzene, 3-bpcd = N,N＇-bis（3- pyridine）cyclohexane-l,4-dicarboxamide, H2NPH = 3-nitrophthalic acid, H2NIPH = 5-nitroisophthalic acid, 5-HaAIP = 5-aminoisophthalic acid] have been synthetized under hydrothermal conditions. Complex 1 displays a one dimensional （1D） chain based on the binuclear [Co2（NPH）2] units and 3-bpeb ligands, which is extended into a three dimensional （3D） supra- molecular framework through hydrogen bonding and n-n stacking interactions. In complex 2, the （3,5）-connected two dimen- sional （2D） layers are constructed from 1D Co-NIPH chains and bidentate-bridging 3-bpeb ligands. Complex 3 is a 2D double layer based on Co-5-H2AIP 2D layers and 3-bpeb pillars. Complex 4 also displays a 2D network, which is constructed from the Co-5-H2AIP 1D double chains and 3-bpcd ligands. Finally, complexes 2--4 are extended into 3D supramolecular frame- works by hydrogen bonding or n-re stacking interactions. The substituent groups of dicarboxylates play an important role in the assembly and structures of the title complexes. In addition, the fluorescent properties of complexes 1-4 and the electrochemi- cal behaviors of 3 and 4 at room temperature have been investigated.
