Nature Chooses Rings: Synthesis of Silicon-Containing Macrocyclic Peroxides

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• 作者：Ashot V. Arzumanyan ; Roman A. Novikov ; Alexander O. Terent鈥檈v ; Maxim M. Platonov ; Valentin G. Lakhtin ; Dmitry E. Arkhipov ; Alexander A. Korlyukov ; Vladimir V. Chernyshev ; Andrew N. Fitch ; Alexander T. Zdvizhkov ; Igor B. Krylov ; Yury V. Tomilov ; Gennady I. Nikishin
• 刊名：Organometallics
• 出版年：2014
• 出版时间：May 12, 2014
• 年：2014
• 卷：33
• 期：9
• 页码：2230-2246
• 全文大小：850K
• 年卷期：v.33,no.9(May 12, 2014)
• ISSN：1520-6041

文摘

The reactions of 1,2-bis(dimethylchlorosilyl)ethane (1), 1,2-bis(dimethylchlorosilyl)ethene (6), and 1,2-bis(dimethylchlorosilyl)ethyne (7) with gem-bis(hydroperoxides) 2a鈥?b>h and 1,1鈥?bis(hydroperoxy)bis(cycloalkyl)peroxides 4a鈥?b>c were found to proceed in an unusual way. Thus, the reactions do not give the expected polymeric peroxides; instead, they produce cyclic silicon-containing peroxides containing 2, 4, or 6 silicon atoms in the ring: 9- (3a鈥?b>h), 12- (5a鈥?b>c), 18- (8, 12), 24- (9, 10), 27- (13), and 36-membered (11) compounds. The size of the rings produced in the reactions increases in the series 1,2-bis(dimethylchlorosilyl)ethane < 1,2-bis(dimethylchlorosilyl)ethene < 1,2-bis(dimethylchlorosilyl)ethyne. The resulting 9- and 12-membered cyclic peroxides are stable under ambient conditions. These compounds were isolated by chromatography and characterized by ¹H, ¹³C, and ²⁹Si NMR spectroscopy, X-ray diffraction, elemental analysis, and high-resolution mass spectrometry. The yields vary from 77 to 95%. Structures of the larger-size rings (18-, 24-, 27-, and 36-membered peroxides) were confirmed by ¹H, ¹³C, and ²⁹Si NMR spectroscopy using 2D (COSY, HSQC, and HMBC), 2D DOSY ¹H, 3D ¹H鈥?sup>29Si HMBC-DOSY NMR experiments, and elemental analysis.