Synthesis of heteroatomic bridged paracyclophanes

Abstract

Heteroatomic bridged paracyclophanes were obtained by two independent synthetic approaches. The required precursors consist of para R₂SiCl (R = Me, iPr) substituted aromatic rings (2 and 4). They were subsequently functionalised by using NH₃, [LiPH₂(dme)] or LiAl(PH₂)₄. In the case of the Me-substituted species 2, the reaction with NH₃ directly yielded the Si₂N bridged paracyclophane 5. The Si₂P incorporated derivative 10 was obtained by lithiation of p-C₆H₄(SiiPr₂PH₂)₂ (9) and subsequent salt metathesis with the chlorosilane 4. The second approach involves the use of GaEt₃ in the formation of four membered (GaPn)₂ cycles (Pn = N, P). p-[C₆H₄{SiiPr₂N(H)GaEt₂}₂]₂ (11) and p-[C₆H₄{SiiPr₂P(H)GaEt₂}₂]₂ (12) represent the first examples of stable (GaPn)₂cis isomers as the trans species did not appear in solution. Although 11 and 12 show a similar coordination pattern, they differ in the orientation of the aromatic systems: in the solid structure, 11 adopts a – for paracyclophanes so far unique – T-shape conformation of the phenyl rings, while 12 shows the predominant coplanar orientation. All cyclophanes were characterized by X-ray diffraction, elemental analysis, NMR and IR spectroscopy.