La[N(SiMe3)2]3 proves to be an efficient catalyst system for the cyclocarbonylation of 1,2-disubstituted benzenes with isocyanates. In this approach, aryl/alkyl isocyanates react with o-phenylenediamine, o-aminophenol...La[N(SiMe3)2]3 proves to be an efficient catalyst system for the cyclocarbonylation of 1,2-disubstituted benzenes with isocyanates. In this approach, aryl/alkyl isocyanates react with o-phenylenediamine, o-aminophenol, o-aminothiophenol, catechols and anilines ortho-substituted by CH2NH2 and CONH2 to form, respectively, the corresponding benzimidazolones, benzoxazolones, benzothiazolones, benzodioxolones, 3,4-dihydroquinazolin-2(1H)-one, and quinazolinediones. These results represent the first example of lanthanide-catalyzed carbonylation. This methodology is also applicable for the preparation of various benzannulated 1,3-diheteroatom cyclic thioketones starting from aryl/alkyl isothiocyanates or CS2 in good to excellent yields. Based on the results of experiments performed using an o-aminobenzamido dianion lanthanide complex, a general mechanism, involving the tandem reaction of two lanthanide-ligand bonds with one heterocumulene molecule, is proposed as well.展开更多
It is known that the first lanthanide （Ln） catalyst used for stereospecific polymeriza-tion of conjugated diene is composed of LnCl3 and R3Al.It initiates stereospecific polymeri-zation of butadiene with a very high...It is known that the first lanthanide （Ln） catalyst used for stereospecific polymeriza-tion of conjugated diene is composed of LnCl3 and R3Al.It initiates stereospecific polymeri-zation of butadiene with a very high cis-1, 4 content（98%）, yet owns poor activity. This paper presents the new results obtained in our laboratory. By adding alcohol tothis binary system （LnCl3-R3Al）, the catalytic activity is greatly enhanced without any losson its high stereospecificity. It is shown that the catalytic activity is dependent on the ratioof its components and their order of addition. Furthermore, we have ascertained that itis the alcohol complex of LnCl3 with a definite composition LnCl3.R3OH, that turns out tobe an active catalyst when treated with R3Al.展开更多
基金supported by the National Natural Science Foundation of China (21132002, 21272038)the National Basic Research Program of China (2011CB825300)
文摘La[N(SiMe3)2]3 proves to be an efficient catalyst system for the cyclocarbonylation of 1,2-disubstituted benzenes with isocyanates. In this approach, aryl/alkyl isocyanates react with o-phenylenediamine, o-aminophenol, o-aminothiophenol, catechols and anilines ortho-substituted by CH2NH2 and CONH2 to form, respectively, the corresponding benzimidazolones, benzoxazolones, benzothiazolones, benzodioxolones, 3,4-dihydroquinazolin-2(1H)-one, and quinazolinediones. These results represent the first example of lanthanide-catalyzed carbonylation. This methodology is also applicable for the preparation of various benzannulated 1,3-diheteroatom cyclic thioketones starting from aryl/alkyl isothiocyanates or CS2 in good to excellent yields. Based on the results of experiments performed using an o-aminobenzamido dianion lanthanide complex, a general mechanism, involving the tandem reaction of two lanthanide-ligand bonds with one heterocumulene molecule, is proposed as well.
文摘It is known that the first lanthanide （Ln） catalyst used for stereospecific polymeriza-tion of conjugated diene is composed of LnCl3 and R3Al.It initiates stereospecific polymeri-zation of butadiene with a very high cis-1, 4 content（98%）, yet owns poor activity. This paper presents the new results obtained in our laboratory. By adding alcohol tothis binary system （LnCl3-R3Al）, the catalytic activity is greatly enhanced without any losson its high stereospecificity. It is shown that the catalytic activity is dependent on the ratioof its components and their order of addition. Furthermore, we have ascertained that itis the alcohol complex of LnCl3 with a definite composition LnCl3.R3OH, that turns out tobe an active catalyst when treated with R3Al.
