In this study, a new zirconium-mediated cycloaddition for preparing dibenzosilole derivatives was developed using siliconbridged diynes and electron-withdrawing alkynes as starting materials. The preparation of silico...In this study, a new zirconium-mediated cycloaddition for preparing dibenzosilole derivatives was developed using siliconbridged diynes and electron-withdrawing alkynes as starting materials. The preparation of silicon-bridged diynes from 1-bromide-2-iodobenzene, terminal alkynes, and dimethyldichlorosilane was also studied. Unlike in the previous synthesis methods, much higher yields of electron-withdrawing group-substituted dibenzosilole derivatives were obtained. In addition, a new synthesis strategy for preparing benzonaphthosilole derivatives using internal alkynes, 1,4-dibromobenzene, and electron-withdrawing alkynes as starting materials is proposed. Compared with previous methods, alkyl, phenyl, and electron-withdrawing groups can be successfully introduced onto aromatic rings, and the positions of these substituents can be easily controlled. The cycloaddition reactions for dibenzosilole and benzonaphthosilole derivatives are highly efficient one-pot processes, and the raw materials are available and easily prepared. Using these new methods, a series of novel multisubstituted dibenzonsilole and benzonaphthosilole derivatives were obtained effectively.展开更多
A novel method for the synthesis of novel silalactone was proposed by iodation and zirconium-mediated cycloaddition of alkynes. 1,1-Dimethyl-4-carboxylatethyl-6,7-diphenyl-5-（trimethylsilyl）-1,3-dihydrobenzo[c][1,2]...A novel method for the synthesis of novel silalactone was proposed by iodation and zirconium-mediated cycloaddition of alkynes. 1,1-Dimethyl-4-carboxylatethyl-6,7-diphenyl-5-（trimethylsilyl）-1,3-dihydrobenzo[c][1,2]oxasilol-3（1 H）-one（compound 1） was obtained and characterized by X-ray single-crystal diffraction. It belongs to the monoclinic system, space group P2_1/n with a = 12.706（3）, b = 10.826（2）, c = 19.407（4） A, β = 91.50（3）°, V = 2668.4（9） A^3, Z = 4, F（000） = 1004, D_c = 1.182 mg/m^3, μ = 0.162 mm^-1, T = 293（2） K, S = 1.129, R = 0.0868 and wR = 0.1607 for 3542 observed reflections with I 〉 2σ（I）. The butadiene derivative, 3,6-di（2-methylphenyl）-4,5-diethylocta-3,5-diene（compound 2）, was synthesized by zirconacyclopentadiene and aryl iodides in the presence of Cu Cl and Pd（PPh3）4. It was characterized by X-ray single-crystal diffraction for the first time, belonging to the monoclinic system, space group C2/c with a = 19.015（4）, b = 7.7697（16）, c = 15.298（3） A, β = 98.24（3）°, V = 2236.8（8） A^3, Z = 8, F（000） = 760, D_c = 1.029 mg/m^3, μ = 0.057 mm^-1, T = 293（2） K, S = 1.100, R = 0.0673 and wR = 0.1391 for 1302 observed reflections with I 〉 2σ（I）.展开更多
基金supported by the National Natural Science Foundation of China(No.21102099)
文摘In this study, a new zirconium-mediated cycloaddition for preparing dibenzosilole derivatives was developed using siliconbridged diynes and electron-withdrawing alkynes as starting materials. The preparation of silicon-bridged diynes from 1-bromide-2-iodobenzene, terminal alkynes, and dimethyldichlorosilane was also studied. Unlike in the previous synthesis methods, much higher yields of electron-withdrawing group-substituted dibenzosilole derivatives were obtained. In addition, a new synthesis strategy for preparing benzonaphthosilole derivatives using internal alkynes, 1,4-dibromobenzene, and electron-withdrawing alkynes as starting materials is proposed. Compared with previous methods, alkyl, phenyl, and electron-withdrawing groups can be successfully introduced onto aromatic rings, and the positions of these substituents can be easily controlled. The cycloaddition reactions for dibenzosilole and benzonaphthosilole derivatives are highly efficient one-pot processes, and the raw materials are available and easily prepared. Using these new methods, a series of novel multisubstituted dibenzonsilole and benzonaphthosilole derivatives were obtained effectively.
文摘A novel method for the synthesis of novel silalactone was proposed by iodation and zirconium-mediated cycloaddition of alkynes. 1,1-Dimethyl-4-carboxylatethyl-6,7-diphenyl-5-（trimethylsilyl）-1,3-dihydrobenzo[c][1,2]oxasilol-3（1 H）-one（compound 1） was obtained and characterized by X-ray single-crystal diffraction. It belongs to the monoclinic system, space group P2_1/n with a = 12.706（3）, b = 10.826（2）, c = 19.407（4） A, β = 91.50（3）°, V = 2668.4（9） A^3, Z = 4, F（000） = 1004, D_c = 1.182 mg/m^3, μ = 0.162 mm^-1, T = 293（2） K, S = 1.129, R = 0.0868 and wR = 0.1607 for 3542 observed reflections with I 〉 2σ（I）. The butadiene derivative, 3,6-di（2-methylphenyl）-4,5-diethylocta-3,5-diene（compound 2）, was synthesized by zirconacyclopentadiene and aryl iodides in the presence of Cu Cl and Pd（PPh3）4. It was characterized by X-ray single-crystal diffraction for the first time, belonging to the monoclinic system, space group C2/c with a = 19.015（4）, b = 7.7697（16）, c = 15.298（3） A, β = 98.24（3）°, V = 2236.8（8） A^3, Z = 8, F（000） = 760, D_c = 1.029 mg/m^3, μ = 0.057 mm^-1, T = 293（2） K, S = 1.100, R = 0.0673 and wR = 0.1391 for 1302 observed reflections with I 〉 2σ（I）.
