The AZARYPHOS Family of Ligands for Ambifunctional Catalysis: Syntheses and Use in Ruthenium-Catalyzed anti-Markovnikov Hydration of Terminal Alkynes
The AZARYPHOS Family of Ligands for Ambifunctional Catalysis: Syntheses and Use in Ruthenium-Catalyzed anti-Markovnikov Hydration of Terminal Alkynes
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DOI：
10.1002/chem.200900563
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发表时间：
2009-01-01
影响因子：
4.3
通讯作者：
Naumov, Pance
中科院分区：
文献类型：
--
作者：
Hintermann, Lukas;Dang, Tuan Thanh;Naumov, Pance
AZARYPHOS（aza-aryl-phosphane）膦配体家族，在配体外围含有一个膦单元和空间屏蔽的氮孤对，被引入作为一种工具，用于通过金属中心和氮孤对在配体球中发展双功能催化。已经开发了一般的合成策略来合成超过25个结构不同的（6-芳基-2-吡啶基）膦（ARPYPHOS）、（6-烷基-2-吡啶基）膦（ALPYPHOS）、4，6-二取代的1，3-二嗪-2-基膦或1，3，5-三嗪-2-基膦、喹唑啉基膦、喹啉基膦等。可扩展的合成分几步进行。将AZARYPHOS配体（L）掺入配合物[RuCp（L）（2）（MeCN）][PF 6]（Cp= CN）中得到了已知活性最高的用于末端炔的反马氏水合的催化剂。电子和空间配位体效应在两个数量级的范围内调节反应动力学。这些结果突出了使用结构不同的配体家族的重要性，在开发合作的双功能催化的过程中，由金属和它的配体。
The family of AZARYPHOS (aza-aryl-phosphane) phosphane ligands, containing a phosphine unit and sterically shielded nitrogen lone pairs in the ligand periphery, is introduced as a tool for developing ambifunctional catalysis by the metal center and nitrogen lone pairs in the ligand sphere. General synthetic strategies have been developed to synthesize over 25 examples of structurally diverse (6-aryl-2pyridyl)phosphanes (ARPYPHOS), (6alkyl-2-pyridyl)phosphanes (ALPYPHOS), 4,6-disubsituted 1,3-diazin-2-ylphosphanes or 1,3,5-triazin-2-ylphosphanes, quinazolinylphosphanes, quinolinylphosphanes, and others. The scalable syntheses proceed in a few steps. The incorporation of AZARYPHOS ligands (L) into complexes [RuCp(L)(2)(MeCN)][PF6] (Cp=cyclopentadienyl) gives catalysts for the anti-Markovnikov hydration of terminal alkynes of the highest known activities. Electronic and steric ligand effects modulate the reaction kinetics over a range of two orders of magnitude. These results highlight the importance of using structurally diverse ligand families in the process of developing cooperative ambifunctional catalysis by a metal and its ligand.