A series of 2-polyfluoroaryl arylacetates were synthesized by a one-pot three-component VNSAr-SNAr reaction of polyfluoroarenes, ethyl 2-chloropropionate, and ortho-substituted nitrobenzenes.
The microwave-assisted coupling reaction of electrondeficient aryl halides with sulfinic acid salts through SNAr-based addition reactions within 5-30 min. No catalysts were required under our conditions.
采用B3LYP/6-311＋G＊＊和MP2/6-311＋G＊＊方法,研究了卤素离子与卤代苯气相SNAr反应（Ar Y＋X-=Ar X＋Y-,X,Y=F,Cl,Br和I）。结果显示,气相里除了X=Y=F反应为分步路径外,其余反应通道都是协同SNAr机理;F离子进攻卤苯SNAr反应无论从动...采用B3LYP/6-311＋G＊＊和MP2/6-311＋G＊＊方法,研究了卤素离子与卤代苯气相SNAr反应（Ar Y＋X-=Ar X＋Y-,X,Y=F,Cl,Br和I）。结果显示,气相里除了X=Y=F反应为分步路径外,其余反应通道都是协同SNAr机理;F离子进攻卤苯SNAr反应无论从动力学（总能垒ΔGb=9.0~17.3 k J/mol）还是热力学上来说都很容易进行,然而Cl、Br和I离子进攻的反应,其MP2吉布斯自由能垒（ΔGb）高达91.3-202.5 k J/mol,因此在气相里很难发生;另外,标题反应的反应性可以通过卤素离子质子亲和能（PA）、最高占据轨道能（EHOMO）、Mulliken电负性（χ）以及Wiberg键级（BO）与NPA电荷（Q）来分析,其中,过渡态里C─Y键的断裂是引起反应能垒升高的主要因素,亲核试剂的亲核能力主要由EHOMO控制,而卤素离子的离去能力由其PA或χ决定。展开更多
A series of multi-(phe nylthio)porphyrinato Ni(Ⅱ) compounds were synthesized without the participation of transition metal catalysts.All of these products were well characterized by 1 H NMR,13C NMR and HRMS.Structure...A series of multi-(phe nylthio)porphyrinato Ni(Ⅱ) compounds were synthesized without the participation of transition metal catalysts.All of these products were well characterized by 1 H NMR,13C NMR and HRMS.Structures of three typical compounds were further confirmed by X-ray single crystal diffraction.Remarkable red shifts were observed in UV-vis absorption spectra of multi-(phenylthio)porphyrinato Ni(Ⅱ) compounds which meet well with the electrochemical data.DFT calculation indicates that the phenylthio groups have strong effects on the frontier orbitals of these molecules.The order of a_(1u)-like and a_(2u)-like orbitals mainly distributed in porphyrin moiety is often inversed in energy when multiphenylthio groups are attached.展开更多
基金supports from the National Natural Science Foundation of China （Nos. 21072057, 21272070）, the Key Project in the National Science ＆ Technology Pillar Program of China in the twelfth five-year plan period （No. 2011BAE06B01-15）, the National Basic Research Program of China （973 Program, No. 2010CB126101）, and the National High Technology Research and Development Program of China （863 Program, 2011AA10A204）.
文摘A series of 2-polyfluoroaryl arylacetates were synthesized by a one-pot three-component VNSAr-SNAr reaction of polyfluoroarenes, ethyl 2-chloropropionate, and ortho-substituted nitrobenzenes.
基金the Municipal Government of Shanghai(No.03DZ19209)Shanghai Hua-Yi Group for financial support.
文摘The microwave-assisted coupling reaction of electrondeficient aryl halides with sulfinic acid salts through SNAr-based addition reactions within 5-30 min. No catalysts were required under our conditions.
文摘采用B3LYP/6-311＋G＊＊和MP2/6-311＋G＊＊方法,研究了卤素离子与卤代苯气相SNAr反应（Ar Y＋X-=Ar X＋Y-,X,Y=F,Cl,Br和I）。结果显示,气相里除了X=Y=F反应为分步路径外,其余反应通道都是协同SNAr机理;F离子进攻卤苯SNAr反应无论从动力学（总能垒ΔGb=9.0~17.3 k J/mol）还是热力学上来说都很容易进行,然而Cl、Br和I离子进攻的反应,其MP2吉布斯自由能垒（ΔGb）高达91.3-202.5 k J/mol,因此在气相里很难发生;另外,标题反应的反应性可以通过卤素离子质子亲和能（PA）、最高占据轨道能（EHOMO）、Mulliken电负性（χ）以及Wiberg键级（BO）与NPA电荷（Q）来分析,其中,过渡态里C─Y键的断裂是引起反应能垒升高的主要因素,亲核试剂的亲核能力主要由EHOMO控制,而卤素离子的离去能力由其PA或χ决定。
基金supported by the National Nature Science Foundation of China (Nos.21702057,21772036,and 21602058)the Scientific Research Fund of Hunan Provincial Science and Technology Department (No.2017JJ3199)+1 种基金Science and Technology Planning Project of Hunan Province (No.2018TP1017)the Opening Fund of Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China)。
文摘A series of multi-(phe nylthio)porphyrinato Ni(Ⅱ) compounds were synthesized without the participation of transition metal catalysts.All of these products were well characterized by 1 H NMR,13C NMR and HRMS.Structures of three typical compounds were further confirmed by X-ray single crystal diffraction.Remarkable red shifts were observed in UV-vis absorption spectra of multi-(phenylthio)porphyrinato Ni(Ⅱ) compounds which meet well with the electrochemical data.DFT calculation indicates that the phenylthio groups have strong effects on the frontier orbitals of these molecules.The order of a_(1u)-like and a_(2u)-like orbitals mainly distributed in porphyrin moiety is often inversed in energy when multiphenylthio groups are attached.
