The Selective Synthesis of Metallanucleosides and Metallanucleotides: A New Tool for the Functionalization of Nucleic Acids

Abstract

Nucleobases team up: the efficient and selective preparation of purine-derived metallanucleosides, metallanucleotides, and metalladinucleotides having M-C bonds (M=Ir(III), Rh(III)) is reported for the first time. The results presented may be applied to the synthesis of functionalized nucleic acids, or DNA/RNA-modified segments.

Nucleobases Having M–C Bonds: An Emerging Bio‐Organometallic Field

“…[13] The methodology employs the dimers [MCl 2 Cp*] 2 (M = Rh, Ir) as metal sources, in dichloromethane at room temperature and in the presence of NaOAc (Scheme 2). [13] The methodology employs the dimers [MCl 2 Cp*] 2 (M = Rh, Ir) as metal sources, in dichloromethane at room temperature and in the presence of NaOAc (Scheme 2).…”

“…[13] The methodology employs the dimers [MCl 2 Cp*] 2 (M = Rh, Ir) as metal sources, in dichloromethane at room temperature and in the presence of NaOAc (Scheme 2). [13] The methodology allows for the preparation of a wide range of substrates, from simple Rh III and Ir III 6-phenylpurine metallacycles to more sophisticated metallanucleosides and metallanucleotides that were obtained as (1:1) diastereomeric mixtures (Scheme 2). All half-sandwich metallacycles prepared (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16) were obtained in very good to excellent yields.…”

“…Under these conditions, the 6-phenylpurine derivatives tested led exclusively to the corresponding fivemembered ring metallacycles 1-16 in a process that involves the coordination of the metal complex to the N1 position of the purine skeleton and the activation of the ortho-phenyl C(sp 2 )-H bond. [13] Scheme 2. The reaction conditions were compatible with the presence of the labile glycosidic bonds, the free OH groups of ribose and deoxyribose derivatives and the phosphate group.…”

“…All half-sandwich metallacycles prepared (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16) were obtained in very good to excellent yields. [13] The compatibility of the formation of the metallacycle with the free N9 position in the purine ring, was also explored. [13] The methodology allows for the preparation of a wide range of substrates, from simple Rh III and Ir III 6-phenylpurine metallacycles to more sophisticated metallanucleosides and metallanucleotides that were obtained as (1:1) diastereomeric mixtures (Scheme 2).…”

“…[13] This iridium metallacycle (65) contains three half-sandwich units and three 6-phenylpurine fragments. [13] This iridium metallacycle (65) contains three half-sandwich units and three 6-phenylpurine fragments.…”