The reaction of
N6,
N9-dimethyladenine (
N6,
N9-Me
2Ade,
1) with methyllithium in aprotic solvents such as tetrahydrofuranand pyridine resulted in the formation of the lithiated adenine [Li(
N6,
N9-Me
2Ade
-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 (
2N6,
N7:
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, Me
3SiCl, and Me
3SnCl resulted in highyields (88-98%) of the formation of the adenine deriatives
N6,
N6,
N9-Me
3Ade
-H (
3),
N6-(SiMe
3)-
N6,
N9-Me
2Ade
-H(
4), and
N6-(SnMe
3)-
N6,
N9-Me
2Ade
-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-Me
2Ade
-H)] (
2) in 90% yield.