Metal-Dependent Reactions of Bulky Metal(II) Amides M[N(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub> with 3,3′-Disubstituted Binaphthols (HO)<sub>2</sub>C<sub>20</sub>H<sub>10</sub>(SiR<sub>3</sub>)<sub>2</sub>-3,3′: Selective Conversion of One Equivalent −OH Group to a Silyl Ether −OSiMe<sub>3</sub>
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The outcome of the reaction of the bulky metal(II) amides M[N(SiMe3)2]2·nTHF (M = Be, Zn, Ge, Sn, n = 0; M = Mg, Ca, n = 2) with (R)-3,3′-bis(trimethylsilyl)-1,1′-bi-2,2′-naphthol ((R)-1) or (S)-3,3′-bis(dimethylphenylsilyl)-1,1′-bi-2,2′-naphthol ((S)-9) depends on the identity of the metal and the nature of the 3,3′-substituents. When M = Be, Zn, or Ge, these amides serve as useful silylation agents that convert only one of the equivalent hydroxyl groups of the binaphthol (R)-1 to a trimethylsilyl ether, whereas the reactions of (R)-1 with the Mg, Ca, or Sn amides generate a polynuclear complex. The reaction pathway for these interconversions was qualitatively monitored using NMR (1H and 9Be) spectroscopy. Treatment of Ge[N(SiMe3)2]2 with (S)-9 yields both a silyl ether and the chelated germanium(II) binaphthoxide (S)-[Ge{O2C20H10(SiMe2Ph)2-3,3′}{NH3}], which was structurally characterized.
