Nature Chooses Rings: Synthesis of Silicon-Containing Macrocyclic Peroxides

Nature Chooses Rings: Synthesis of Silicon-Containing Macrocyclic Peroxides Full article

Journal

Organometallics
ISSN: 1520-6041 , E-ISSN: 0276-7333

Output data

Year: 2014, Volume: 33, Number: 9, Pages: 2230-2246 Pages count : 17 DOI: 10.1021/om500095x

Authors

Arzumanyan Ashot V. ¹ , Novikov Roman A. ¹ , Terent’ev Alexander O. ¹ , Platonov Maxim M. ¹ , Lakhtin Valentin G. ² , Arkhipov Dmitry E. ^3,4 , Korlyukov Alexander A. ^3,4 , Chernyshev Vladimir V. ^5,6 , Fitch Andrew N. ⁷ , Zdvizhkov Alexander T. ¹ , Krylov Igor B. ¹ , Tomilov Yury V. ¹ , Nikishin Gennady I. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation
2	State Research Institute for Chemistry and Technology of Organoelement Compounds, 38 shosse Entuziastov, Moscow 111123 Russian Federation
3	A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova ul, Moscow 119991 Russian Federation
4	Pirogov Russian National Research Medical University, Ostrovitianov str. 1, Moscow 117997 Russian Federation
5	Department of Chemistry, M. V. Lomonosov Moscow State University, 1-3 Leninskie Gory, Moscow 119991 Russian Federation
6	A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky prospect, Moscow 119071 Russian Federation
7	European Synchrotron Radiation Facility, B.P.220-38043, Grenoble, CEDEX, France

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–h and 1,1′-bis(hydroperoxy)bis(cycloalkyl)peroxides 4a–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–h), 12- (5a–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–29Si HMBC-DOSY NMR experiments, and elemental analysis.

Arzumanyan A.V. , Novikov R.A. , Terent’ev A.O. , Platonov M.M. , Lakhtin V.G. , Arkhipov D.E. , Korlyukov A.A. , Chernyshev V.V. , Fitch A.N. , Zdvizhkov A.T. , Krylov I.B. , Tomilov Y.V. , Nikishin G.I.
Nature Chooses Rings: Synthesis of Silicon-Containing Macrocyclic Peroxides
Organometallics. 2014. V.33. N9. P.2230-2246. DOI: 10.1021/om500095x WOS Scopus OpenAlex

≡ Web of science:	WOS:000335939900014
≡ Scopus:	2-s2.0-84900441759
≡ OpenAlex:	W2072404916