Synthesis of Carbamoylphosphates from Isocyanates Catalyzed by Rare-Earth-Metal Alkyl Complexes with a Silicon-Linked Diarylamido Ligand
Synthesis of Carbamoylphosphates from Isocyanates Catalyzed by Rare-Earth-Metal Alkyl Complexes with a Silicon-Linked Diarylamido Ligand
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稀土金属烷基配合物与硅连接的二芳基酰胺配体催化异氰酸酯合成氨基甲酰磷酸盐
DOI：
10.1021/acs.organomet.0c00627
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发表时间：
2020
期刊：
影响因子：
2.8
通讯作者：
Qi Yawen
中科院分区：
文献类型：
--
作者：
Zhu Xiancui;Guo Dianjun;Zhang Yiwei;Wei Yun;Zhou Shuangliu;Xu Mengchen;Wang Shaowu;Yang Yuanqing;Qi Yawen
合成并表征了具有硅连接二芳基酰胺配体的中性稀土金属单烷基配合物和阴离子稀土金属二烷基配合物，并开发了它们对亚磷酸二烷基酯与异氰酸酯加成的催化活性。稀土金属三烷基配合物 RE(CH2SiMe3)3(THF)2 与硅连接的二芳基胺配体在己烷中反应，以良好的收率得到中性稀土金属单烷基配合物 LRE(CH2SiMe3)(THF)2(RE = Y (1), Er (2);L= (Me2Si)(2,6-iPr2C6H3N)2)。通过H2L、正丁基锂和无水RECl3的盐复分解反应合成了双核稀土金属氯化物[LRE(μ-Cl)(THF)2]2(RE=Y(3),Er(4))。用 4 当量的 LiCH2SiMe3 在甲苯中处理稀土金属氯化物，生成相应的离散异双金属稀土金属二烷基配合物 LRE(CH2SiMe3)2(THF)Li(THF)4(RE = Y (5), Er (6))。进一步的研究表明，在0.1 mol%稀土金属单烷基或二烷基配合物作为催化剂存在下，在室温下无溶剂条件下，亚磷酸二烷基酯与各种烷基和芳基取代的异氰酸酯加成，在5 min内以高至优异的收率（高达99%）高效合成了多种氨基甲酰磷酸酯，为快速构建C-P键提供了一种绿色高效的方法，以提供各种氨基甲酰磷酸衍生物。
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)2with a silicon-linked diarylamine ligand inn-hexane afforded the neutral rare-earth-metal monoalkyl complexesLRE(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 LiCH2SiMe3in toluene generated the corresponding discrete heterobimetallic rare-earth-metal dialkyl complexesLRE(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.