Synthesis, Characterization, and Reactivity of [Li(N6,N9-Me2Ade-H)]: A Structurally Characterized Lithiated Adenine
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- 作者：Thomas Krü ; ger ; Tobias Rü ; ffer ; Heinrich Lang ; Christoph Wagner ; Dirk Steinborn
- 刊名：Inorganic Chemistry
- 出版年：2008
- 出版时间：February 4, 2008
- 年：2008
- 卷：47
- 期：3
- 页码：1190 - 1195
- 全文大小：180K
- 年卷期：v.47,no.3(February 4, 2008)
- ISSN：1520-510X
文摘
The reaction of N6,N9-dimethyladenine (N6,N9-Me2Ade, 1) with methyllithium in aprotic solvents such as tetrahydrofuranand pyridine resulted in the formation of the lithiated adenine [Li(N6,N9-Me2Ade-H)] (2) that was isolated as highlyair and moisture sensitive tetrahydrofuran (2·1/4THF) and pyridine (2·py) adducts in excellent yields (>90%). Theidentities of 2·1/4THF and 2·py were confirmed by 1H and 13C NMR spectroscopy. In crystals of 2·3/2py, thedimethyladeninato ligand exhibited a chelating and bridging coordination mode (
hars/kappa.gif" BORDER=0 >2N6,N7:hars/kappa.gif" BORDER=0 >N3) resulting in a 1-Dpolymeric chain-like structure in which the tetrahedral coordination sphere of the lithium atoms was completed bya pyridine molecule. Reactions of 2·1/4THF with electrophiles such as MeI, Me3SiCl, and Me3SnCl resulted in highyields (88-98%) of the formation of the adenine deriatives N6,N6,N9-Me3Ade-H (3), N6-(SiMe3)-N6,N9-Me2Ade-H(4), and N6-(SnMe3)-N6,N9-Me2Ade-H (5), respectively. Compounds 3-5 were characterized by 1H, 13C, 29Si (4),and 119Sn (5) NMR spectroscopy and MS investigations, and the stannylated derivative 5 also was characterizedby single-crystal diffraction analysis exhibiting a mononuclear structure. The reaction of the stannylated adenine 5with n-BuLi in n-hexane proceeded in the sense of a tin-lithium transmetalation reaction yielding the solvent-freelithium adeninate [Li(N6,N9-Me2Ade-H)] (2) in 90% yield.
hars/kappa.gif" BORDER=0 >2N6,N7:hars/kappa.gif" BORDER=0 >N3) resulting in a 1-Dpolymeric chain-like structure in which the tetrahedral coordination sphere of the lithium atoms was completed bya pyridine molecule. Reactions of 2·1/4THF with electrophiles such as MeI, Me3SiCl, and Me3SnCl resulted in highyields (88-98%) of the formation of the adenine deriatives N6,N6,N9-Me3Ade-H (3), N6-(SiMe3)-N6,N9-Me2Ade-H(4), and N6-(SnMe3)-N6,N9-Me2Ade-H (5), respectively. Compounds 3-5 were characterized by 1H, 13C, 29Si (4),and 119Sn (5) NMR spectroscopy and MS investigations, and the stannylated derivative 5 also was characterizedby single-crystal diffraction analysis exhibiting a mononuclear structure. The reaction of the stannylated adenine 5with n-BuLi in n-hexane proceeded in the sense of a tin-lithium transmetalation reaction yielding the solvent-freelithium adeninate [Li(N6,N9-Me2Ade-H)] (2) in 90% yield.