当前位置：
X-MOL 学术
›
Organometallics
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Synthesis of Carbamoylphosphates from Isocyanates Catalyzed by Rare-Earth-Metal Alkyl Complexes with a Silicon-Linked Diarylamido Ligand
Organometallics ( IF 2.5 ) Pub Date : 2020-12-11 , DOI: 10.1021/acs.organomet.0c00627 Xiancui Zhu 1 , Dianjun Guo 1 , Yiwei Zhang 1 , Yun Wei 1 , Shuangliu Zhou 1 , Mengchen Xu 1 , Shaowu Wang 1, 2 , Yuanqing Yang 1 , Yawen Qi 1
Organometallics ( IF 2.5 ) Pub Date : 2020-12-11 , DOI: 10.1021/acs.organomet.0c00627 Xiancui Zhu 1 , Dianjun Guo 1 , Yiwei Zhang 1 , Yun Wei 1 , Shuangliu Zhou 1 , Mengchen Xu 1 , Shaowu Wang 1, 2 , Yuanqing Yang 1 , Yawen Qi 1
Affiliation
|
Neutral rare-earth-metal monoalkyl complexes and anionic rare-earth-metal dialkyl complexes with a silicon-linked diarylamido ligand were synthesized and characterized, and their catalytic activities toward the additions of dialkyl phosphites to isocyanates were developed. Reactions of rare-earth-metal trialkyl complexes RE(CH2SiMe3)3(THF)2 with a silicon-linked diarylamine ligand in n-hexane afforded the neutral rare-earth-metal monoalkyl complexes LRE(CH2SiMe3)(THF)2 (RE = Y (1), Er (2); L = (Me2Si)(2,6-iPr2C6H3N)2) in good yields. The dinuclear rare-earth-metal chlorides [LRE(μ-Cl)(THF)2]2 (RE = Y (3), Er (4)) were synthesized by the salt metathesis reaction of H2L, nBuLi, and anhydrous RECl3. Treatment of the rare-earth-metal chlorides with 4 equiv of LiCH2SiMe3 in toluene generated the corresponding discrete heterobimetallic rare-earth-metal dialkyl complexes LRE(CH2SiMe3)2(THF)Li(THF)4 (RE = Y (5), Er (6)). Further investigation showed that a wide variety of carbamoylphosphates were efficiently synthesized in high to excellent yields (up to 99%) via the additions of dialkyl phosphites to various alkyl- and aryl-substituted isocyanates in the presence of 0.1 mol % rare-earth-metal monoalkyl or dialkyl complexes as catalysts under solvent-free conditions at room temperature within 5 min, which provided a green and highly efficient method for the rapid construction of C–P bonds to afford various carbamoylphosphate derivatives.
中文翻译：
稀土-金属硅烷基二芳基酰胺配体配合物催化异氰酸酯合成氨基甲酸酯磷酸酯
合成和表征了具有硅连接的二芳基酰胺配体的中性稀土金属单烷基络合物和阴离子稀土金属二烷基络合物，并开发了它们对亚磷酸二烷基酯加至异氰酸酯的催化活性。稀土类金属的反应的三烷基络合物RE（CH 2森达3）3（THF）2在硅联二芳基胺配体Ñ己烷，得到中性稀土类金属单烷基络合物大号RE（CH 2森达3） （THF）2（RE = Y（1），Er（2）; L =（Me 2Si）（2,6- i Pr 2 C 6 H 3 N）2）的产率很高。通过H 2 L，n BuLi，的盐复分解反应合成了双核稀土金属氯化物[ L RE（μ- Cl）（THF）2 ] 2（RE = Y（3），Er（4））。和无水RECl 3。用4当量的LiCH 2 SiMe 3在甲苯中处理稀土金属氯化物，生成相应的离散的异双金属稀土金属二烷基络合物L RE（CH2 SiMe 3）2（THF）Li（THF）4（RE = Y（5），Er（6））。进一步的研究表明，在存在0.1 mol％稀土金属的情况下，通过将亚磷酸二烷基酯添加到各种烷基和芳基取代的异氰酸酯中，可以高产率至高产率（高达99％）高效合成各种氨基甲酸酯磷酸酯。单烷基或二烷基络合物在室温下5分钟内在无溶剂条件下于室温下作为催化剂，为快速构建C-P键提供各种绿色的氨基甲酰基磷酸酯衍生物提供了一种绿色高效的方法。
更新日期：2020-12-28
中文翻译：
稀土-金属硅烷基二芳基酰胺配体配合物催化异氰酸酯合成氨基甲酸酯磷酸酯
合成和表征了具有硅连接的二芳基酰胺配体的中性稀土金属单烷基络合物和阴离子稀土金属二烷基络合物，并开发了它们对亚磷酸二烷基酯加至异氰酸酯的催化活性。稀土类金属的反应的三烷基络合物RE（CH 2森达3）3（THF）2在硅联二芳基胺配体Ñ己烷，得到中性稀土类金属单烷基络合物大号RE（CH 2森达3） （THF）2（RE = Y（1），Er（2）; L =（Me 2Si）（2,6- i Pr 2 C 6 H 3 N）2）的产率很高。通过H 2 L，n BuLi，的盐复分解反应合成了双核稀土金属氯化物[ L RE（μ- Cl）（THF）2 ] 2（RE = Y（3），Er（4））。和无水RECl 3。用4当量的LiCH 2 SiMe 3在甲苯中处理稀土金属氯化物，生成相应的离散的异双金属稀土金属二烷基络合物L RE（CH2 SiMe 3）2（THF）Li（THF）4（RE = Y（5），Er（6））。进一步的研究表明，在存在0.1 mol％稀土金属的情况下，通过将亚磷酸二烷基酯添加到各种烷基和芳基取代的异氰酸酯中，可以高产率至高产率（高达99％）高效合成各种氨基甲酸酯磷酸酯。单烷基或二烷基络合物在室温下5分钟内在无溶剂条件下于室温下作为催化剂，为快速构建C-P键提供各种绿色的氨基甲酰基磷酸酯衍生物提供了一种绿色高效的方法。
京公网安备 11010802027423号