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Osmium-Promoted σ-Bond Activation Reactions on Nucleosides
Organometallics ( IF 2.8 ) Pub Date : 2020-01-15 , DOI: 10.1021/acs.organomet.9b00693
Marta Valencia 1 , Alba D. Merinero 1 , Carmen Lorenzo-Aparicio 1 , Mar Gómez-Gallego 1 , Miguel A. Sierra 1 , Beatriz Eguillor 2 , Miguel A. Esteruelas 2 , Montserrat Oliván 2 , Enrique Oñate 2
Affiliation  

OsH6(PiPr3)2 has been used to selectively activate C–H, O–H, and C–C sigma bonds in nucleobases and nucleosides, including derivatives of 6-phenylpurine and 4-phenylpyrimidine, leading to cyclometalated mononuclear Os–trihydride complexes, in excellent yields and as single products. Additionally, OsH6(PiPr3)2 promotes the efficient dehydrogenative decarbonylation of primary alcohols in nucleosides having unprotected sugar moieties. The incorporation of OsH2Cl2(PiPr3)2 in the structure of cyclometalated Ir(III) and Rh(III) half-sandwich complexes derived from nucleosides allows the preparation of a class of heterobimetallic bioorganometallic complexes having at least one M–C bond. These methodologies could be used in the future as a way for the orthogonal functionalization of oligonucleotides.

中文翻译:

Nu在核苷上促进的σ键活化反应

OsH 6(P i Pr 32已被用于选择性激活核碱基和核苷中的C–H,OH–和C–C sigma键,包括6-苯基嘌呤和4-苯基嘧啶的衍生物,从而形成环金属化的单核Os -三氢化物配合物,收率极高,可作为单一产品使用。另外,OsH 6(P i Pr 32促进具有未保护的糖部分的核苷中伯醇的有效脱氢脱羰作用。OsH 2 Cl 2(P i Pr 32的引入在环金属化的Ir(III)和Rh(III)核苷半夹心络合物的结构中,可以制备一类具有至少一个M-C键的异双金属生物有机金属络合物。这些方法可在将来用作寡核苷酸正交功能化的方法。
更新日期:2020-01-15
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