Synthesis and Characterization of a Variety of α,ω-Bisacylpolysilanes-A Study on Reactivity and Accessibility

In this study, a variety of α,ω-bisacylpolysilanes were synthesized via two synthetic protocols. The first method for obtaining these compounds is based on the substitution reaction of bromine either on silica gel or by the use of silver salts. Surprisingly, instead of the expected bromine substitution product PhC(O)(SiMe₂)₂C(O)Ph 4a, we found the formation of the diastereomer PhC(O)(SiMe₂)₂CBrPhOCBrPh(SiMe₂)₂C(O)Ph 4b indicating a more complex reaction cascade. On the other hand, the phenylated compound 3b yielded the expected bromine substitution product PhC(O)(SiPh₂)₂C(O)Ph 4c. For the second protocol, we utilized the Corey-Seebach approach to isolate other representatives of this compound class. We found that the substituents at the α-silicon atoms influence the selectivity of the dethioketalization. While the ethylated and phenylated disilanes 5b,c yield the expected bisacyldisilanes 6a,b, the methylated disilane 4a undergoes a BF₃-induced Si-Si bond breakage followed by an intermolecular sila-aldol reaction. This hitherto unknown sila-aldol reaction results in the formation of the enantiomer PhC(O)SiMe₂C(OMe)PhSiMe₂F 6c in excellent yields. All isolated compounds were analyzed by a combination of NMR spectroscopy, ultraviolet-visible (UV-vis) spectroscopy, single-crystal X-ray crystallography, and mass spectrometry. Furthermore, the photochemical pathways of two representative examples (4b,c) were examined.