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Imine-Palladacycles as Phosphine-Free Precatalysts for Low-Temperature Suzuki–Miyaura Synthesis of Nucleoside Analogues in Aqueous Media
Organometallics ( IF 2.8 ) Pub Date : 2020-11-09 , DOI: 10.1021/acs.organomet.0c00580
José Luis Serrano 1 , Luis García 1 , José Pérez 1 , Pedro Lozano 2 , Jevy Correia 3 , Santosh Kori 3, 4 , Anant R. Kapdi 3 , Yogesh S. Sanghvi 5
Affiliation  

The synthesis and characterization of new water-soluble dinuclear palladacycles of the general formula [{Pd(R-C^N-SO3Na)(μ-AcO)}2] (R = H (1), OMe (2), Cl (3)) incorporating an ortho-metalated sodium 4-(N-benzylideneamino)benzenesulfonate moiety is reported. These complexes have been revealed to be excellent phosphine-free catalysts for the synthesis of functionalized nucleoside analogues involving a low-temperature Suzuki–Miyaura coupling of 5-iodo-2′-deoxyuridine with different arylboronic acids in neat water. The potential of 13 as synthetic precursors was also tested, and bridging acetates were cleaved by reaction with neutral PPh3, yielding the corresponding mononuclear derivatives [Pd(R-C^N-SO3Na)(AcO)(PPh3)] (R = H (4), MeO (5), Cl (6)). Analytical and spectroscopic techniques confirmed the proposed formulas and reactivities reported for complexes 16. Structural characterization by X-ray diffraction of single crystals grown from samples of 4 and 6 produced the unexpected but valuable crystallization-mediated compounds 4cm and 6cm that also supported the results presented here.

中文翻译:

亚胺-Paladacycles作为低温水中铃木-宫浦合成核苷类似物的无磷预催化剂

通式[{Pd(RC ^ N-SO 3 Na)(μ-AcO)} 2 ](R = H(1),OMe(2),Cl(3))报道了结合有金属化的4-(N-亚苄基氨基)苯磺酸钠部分。这些配合物已被证明是用于合成功能化核苷类似物的极佳无膦催化剂,涉及在纯净水中5-碘-2'-脱氧尿苷与不同芳基硼酸的低温Suzuki-Miyaura偶联。的潜在的1 - 3还测试了合成前体,并通过与中性PPh 3反应裂解了桥接的乙酸盐,得到了相应的单核衍生物[Pd(RC ^ N-SO 3 Na)(AcO)(PPh 3)](R = H(4) ,MeO(5),Cl(6))。分析和光谱技术证实所提出的公式和反应性报道的络合物1 - 6。通过X射线衍射对从46样品中生长的单晶进行结构表征可产生出乎意料但有价值的结晶介导化合物4cm6cm 这也支持此处介绍的结果。
更新日期:2020-12-28
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