Two new macrocyclic complexes with C-methyl substituents on the framework, namely, [CuL]（ClO4）2 （L = 5,12-dimethyl-1,8-dihydroxyethyl-1,3,6,8,10,13-hexaazacyclotetradecane） 1 and [NiL]（ClO4）2 2, have been synthe...Two new macrocyclic complexes with C-methyl substituents on the framework, namely, [CuL]（ClO4）2 （L = 5,12-dimethyl-1,8-dihydroxyethyl-1,3,6,8,10,13-hexaazacyclotetradecane） 1 and [NiL]（ClO4）2 2, have been synthesized and structurally characterized through X-ray diffraction analysis. Also, crystal structure of [CuL^1]（ClO4）2 （L^1 = 1,8-dimethyl- 1,3,6,8, [ 0,13- hexaazacyclotetradecane） 3 has been determined. Crystal data for 1： C14H32C12CuN6O10, Mr = 578.90, monoclinic, P2 1/n, α = 8.3529（11）, b = 10.8105（17）, c = 13.3709（17） ,A, β = 105.189（10）°, V= 1165.2（3） A3, Z = 2, Dc = 1.650 g/cm^3, F（000） = 602, λ（MoKct） = 0.71073 A,μ = 1.229 mm ^-1, R = 0.0474 and wR = 0.0895 for 2771 observed reflections （I 〉 2σ（Ⅰ））. Crystal data for 2： C14H32C12N6NiO10, Mr = 574.07, monoclinic, P2 1/c, a = 8.3636（12）, b = 12.997（2）, c = 10.764（2） A, β = 99.31（2）°, V = 1154.7（3） A^3, Z = 2, DC = 1.651 g/cm^3, F（000） = 600, λ（MoKa） = 0.71073 A,μ = 1. 134 mm^-1, R = 0.0380 and wR = 0.0796 for 2670 observed reflections （i 〉 2σ（Ⅰ））. Crystal data for 3： C 10H26Cl2CuN6O8, Mr = 492.81, monoclinic, P2 1/n, a = 8.4860（17）, b = 8.6320（17）, c = 12.662（3） ,A,β = 103.40（3）°, V = 902.2（3）A^3, Z = 2, Dc = 1.814 g/cm^3, F（000） = 510, λ（MoKa） = 0.71073A, μ = 1.562 mm^-1, R = 0.0505 and wR = 0.1061 for 1967 observed reflections （I〉 2σ（Ⅰ））. Complexes 1 and 2 are isostructural with the metal ions situated at the inversion center/Hydrogen bonds between O atoms of pendant and perchlorate anion give rise to a two-dimensional supramolecular layer. The Cu（Ⅱ） ions of compounds 1 and 3 adopt distorted axially-elongated octahedral coordinate geometry, and the nickel（Ⅱ） ion in complex 2 is four-coordinated with a square-planar configuration.展开更多
The use of thallium(I) hydroxide (TlOH) as a base is known to extremely accelerate the Suzuki-Miyaura cross-coupling reaction using organoboronic acid or organoboronic acid ester as a substrate. Here, we investigated ...The use of thallium(I) hydroxide (TlOH) as a base is known to extremely accelerate the Suzuki-Miyaura cross-coupling reaction using organoboronic acid or organoboronic acid ester as a substrate. Here, we investigated the effects of TlOH by comparing with other conventional bases such as KOH, K2CO3, and CsF for Pd0-mediated rapid cross-coupling reactions between CH3I and organoborane reagents, such as phenyl-, (Z)-4-benzyloxy-2-butenyl-, and benzylboronic acid pinacol esters under the conditions CH3I/borane/Pd0/base (1:40:1:3) in THF/H2O or DMF/H2O for 5 min with an aim to fabricate a PET tracer efficiently. Consequently, however, the use of TlOH was much less efficient than the other bases for the acceleration of cross-coupling reactions. Thus, it was reconfirmed that the milder and non-toxic conditions using K2CO3 or CsF so far developed by our group were most appropriate for the rapid C-methylations.展开更多
基金Supported by the National Natural Science Foundation of China (20201008)
文摘Two new macrocyclic complexes with C-methyl substituents on the framework, namely, [CuL]（ClO4）2 （L = 5,12-dimethyl-1,8-dihydroxyethyl-1,3,6,8,10,13-hexaazacyclotetradecane） 1 and [NiL]（ClO4）2 2, have been synthesized and structurally characterized through X-ray diffraction analysis. Also, crystal structure of [CuL^1]（ClO4）2 （L^1 = 1,8-dimethyl- 1,3,6,8, [ 0,13- hexaazacyclotetradecane） 3 has been determined. Crystal data for 1： C14H32C12CuN6O10, Mr = 578.90, monoclinic, P2 1/n, α = 8.3529（11）, b = 10.8105（17）, c = 13.3709（17） ,A, β = 105.189（10）°, V= 1165.2（3） A3, Z = 2, Dc = 1.650 g/cm^3, F（000） = 602, λ（MoKct） = 0.71073 A,μ = 1.229 mm ^-1, R = 0.0474 and wR = 0.0895 for 2771 observed reflections （I 〉 2σ（Ⅰ））. Crystal data for 2： C14H32C12N6NiO10, Mr = 574.07, monoclinic, P2 1/c, a = 8.3636（12）, b = 12.997（2）, c = 10.764（2） A, β = 99.31（2）°, V = 1154.7（3） A^3, Z = 2, DC = 1.651 g/cm^3, F（000） = 600, λ（MoKa） = 0.71073 A,μ = 1. 134 mm^-1, R = 0.0380 and wR = 0.0796 for 2670 observed reflections （i 〉 2σ（Ⅰ））. Crystal data for 3： C 10H26Cl2CuN6O8, Mr = 492.81, monoclinic, P2 1/n, a = 8.4860（17）, b = 8.6320（17）, c = 12.662（3） ,A,β = 103.40（3）°, V = 902.2（3）A^3, Z = 2, Dc = 1.814 g/cm^3, F（000） = 510, λ（MoKa） = 0.71073A, μ = 1.562 mm^-1, R = 0.0505 and wR = 0.1061 for 1967 observed reflections （I〉 2σ（Ⅰ））. Complexes 1 and 2 are isostructural with the metal ions situated at the inversion center/Hydrogen bonds between O atoms of pendant and perchlorate anion give rise to a two-dimensional supramolecular layer. The Cu（Ⅱ） ions of compounds 1 and 3 adopt distorted axially-elongated octahedral coordinate geometry, and the nickel（Ⅱ） ion in complex 2 is four-coordinated with a square-planar configuration.
文摘The use of thallium(I) hydroxide (TlOH) as a base is known to extremely accelerate the Suzuki-Miyaura cross-coupling reaction using organoboronic acid or organoboronic acid ester as a substrate. Here, we investigated the effects of TlOH by comparing with other conventional bases such as KOH, K2CO3, and CsF for Pd0-mediated rapid cross-coupling reactions between CH3I and organoborane reagents, such as phenyl-, (Z)-4-benzyloxy-2-butenyl-, and benzylboronic acid pinacol esters under the conditions CH3I/borane/Pd0/base (1:40:1:3) in THF/H2O or DMF/H2O for 5 min with an aim to fabricate a PET tracer efficiently. Consequently, however, the use of TlOH was much less efficient than the other bases for the acceleration of cross-coupling reactions. Thus, it was reconfirmed that the milder and non-toxic conditions using K2CO3 or CsF so far developed by our group were most appropriate for the rapid C-methylations.
