Reduction of Organosilicon Peroxides: Ring Contraction and

Article pubs.acs.org/Organometallics

Reduction of Organosilicon Peroxides: Ring Contraction and Cyclodimerization Ashot V. Arzumanyan,†,‡ Alexander O. Terent’ev,*,† Roman A. Novikov,† Valentin G. Lakhtin,§ Michail S. Grigoriev,∥ and Gennady I. Nikishin† †

N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation ‡ A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova ul, Moscow 119991, Russian Federation § State Scientific Research Institute of Chemistry and Technology of Organoelement Compounds, 38 Shosse Entuziastov, 111123 Moscow, Russian Federation ∥ A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Radiochemistry Department, Russian Academy of Sciences, 40 Obruchev st., 117342 Moscow, Russian Federation S Supporting Information *

ABSTRACT: The reduction of 1,2,7,8-tetraoxa-3,6-disilonanes is accompanied by the selective transformation of two SiOOC moieties into SiOC moieties, resulting in contraction of the nine-membered ring bis-peroxide to a previously unknown class of seven-membered-ring acetals, 1,6-dioxa-2,5-disilepanes. The reduction of six-membered cyclic peroxide proceeds differently and affords four- and eight-membered rings. As a result, silyl ethers of gem-diols, which do not exist in the free form, are produced.

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observed earlier in the reduction of peroxides with SiOOC18 and SiOOSi fragments.18c,d,e,19 Trialkyl- and triphenylphosphines were employed as reducing agents. For instance, the reduction of norbornanone peroxysilyl ether with Ph3P transforms the SiOOC group into a SiOC group.18a,b Triisopropylphopshine selectively reduces tert-butyltrimethylsilyl peroxide to the tert-butyltrimethylsilyl ether.18d The products of ozonolysis of the silyl allylic alcohol and their ethers were reduced to optically active triols using Me3P.18e Previously we found that 1,2,4,5,7,8-hexaoxa-3-silonanes were selectively reduced to the 1,3,5,6-tetraoxa-2-silepanes.20 In this work20 the reduction of SiOOC groups to SiOC in the presence of the COOC moiety within a single molecule was performed for the first time. In the present work, our studies of the reduction of silicon-containing peroxides were extended. We found that this process can not only give ring contraction cyclic products (from nine to seven and from six to four), but can also give ring enlargement cyclic products (from six to eight).

INTRODUCTION Organic peroxides are widely used in laboratory practice and in industry as polymerization initiators, oxidants, autoxidation products, initiators of free radical reactions, and synthetic intermediates.1 In the last decades, peroxides have gained attention in medicine and pharmacology due to the fact that for these compounds, particularly those having a cyclic ring, substantial antimalarial,2 anthelmintic,3 and antitumor activities4 were found. Silicon-containing peroxides are applied for similar purposes, for the initiation of free radical processes,5 hydroxylation of aromatic compounds,6 formation of other peroxides,7 use in thermal reactions,8 and the synthesis of five-,9 six-,9e,10,11 and seven-membered9e,12,13 cyclic peroxides. Fleming 14 and Tamao−Kumada15 reactions follow through intermediate formation of Si−O−O peroxides. The basic principles of the Si−O−O chemistry are the object of numerous works.16 Nevertheless, the number of effective methods for Si−O− O−R peroxide synthesis is considerably limited in comparison with that for carbon-containing peroxides. Several reviews have been devoted to the physicochemical and chemical properties of organosilicon peroxides.17 The reduction reactions of organosilicon cyclic peroxides, in particular, have been scarcely studied.18−20 In this work, we study a rare type of reduction, resulting in the removal of one oxygen atom from SiOOR to yield an SiOR fragment. Some transformations of this type have been © 2016 American Chemical Society

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RESULTS AND DISCUSSION Reduction of Nine-Membered Cyclic Si Peroxides to Seven-Membered Cyclic Si Ethers of gem-Diols. The work was carried out in several steps. First, the reaction Received: February 18, 2016 Published: May 12, 2016 1667

DOI: 10.1021/acs.organomet.6b00129 Organometallics 2016, 35, 1667−1673

Article

Organometallics

tert-butylcyclohexanone in the reaction with di-tert-butyl sulfide (But2S). Under the optimized conditions found for the synthesis of 2d using Ph3P in a slight excess as the reducing agent (the Ph3P to 1,2,7,8-tetraoxa-3,6-disilonane molar ratio was 2.1:1), we performed the reduction of compounds 1a−g containing a cycloalkyl ring with different sizes (C5−C7 and C12) and Me and But substituents in different positions. The reactions were performed at room temperature for 5−9 h to give complete conversion of 1a−g (Table 2).

conditions and agents for the selective preparation of sevenmembered compounds 2a−g from nine-membered peroxides 1a−g were studied. The nine-membered peroxides 1a−g were obtained through the reaction of gem-bis-hydroperoxides with 1,2-bis(dimethylchlorosilyl)ethane.21 Then, we estimated the applicability of these conditions to the reduction of the related peroxides 1a−c,e−g (Scheme 1). Scheme 1. Reduction of 1,2,7,8-Tetraoxa-3,6-disilonanes 1a−g to 1,6-Dioxa-2,5-disilepanes 2a−g

Table 2. 1,6-Dioxa-2,5-disilepanes 2a−g Prepared by the Reduction of 1,2,7,8-Tetraoxa-3,6-disilonanes 1a−g with Ph3Pa

The reduction conditions were optimized by studying the synthesis of Si ether 2d from Si peroxide 1d in different solvents using such reducing agents as phosphines, phosphites, and sulfur-containing compounds (Table 1). Table 1. Influence of the Reductant and the Solvent on the Yield of 1,6-Dioxa-2,5-disilepane 2d Obtained by the Reduction of 1,2,7,8-Tetraoxa-3,6-disilonane 1da a

General procedure unless specified otherwise: a solution of Ph3P (0.351 g, 1.34 mmol) in Et2O (3.5 mL) was added to a stirred solution of tetraoxadisilonane 1a−g (0.176−0.239 g, 0.638 mmol) in Et2O (2 mL) over 2−3 min at 20−25 °C, and then the stirring was continued for 5−9 h. bA solution of bis(dimethylchlorosilyl)ethane (0.137 g, 0.638 mmol) in Et2O (1.5 mL) was added to a stirred solution of 1,1bis(hydroperoxy)-4-tert-butylcyclohexane (0.130 g, 0.638 mmol) and imidazole (0.091 g, 1.34 mmol, molar ratio 2.1:1 mol of peroxide) in Et2O (4 mL), over 2−3 min at 20−25 °C, and then the stirring was continued for 1.5 h. After that a solution of Ph3P (0.351 g, 1.34 mmol) in Et2O (3.5 mL) was added over 2−3 min at 20−25 °C, and then the mixture was stirred for 8 h.

reductant

yield of 2d, %

(PriO)3P

Bu3P

Ph3P

NH2C(S) NH2

But2S

36

47

73, 58,b tracesc

0

0

a

General procedure unless specified otherwise: a solution of a reducing agent (0.101−0.351 g, 1.34 mmol) in Et2O (3.5 mL) was added to a stirred solution of 1d (0.221 g, 0.638 mmol) in Et2O (2 mL) at 20−25 °C for 2−3 min, and then the stirring was continued for 8 h. bTHF as the solvent. cCH2Cl2 as the solvent.

1,6-Dioxa-2,5-disilepanes 2a were synthesized in yields from 47 to 73%. The nature of substituents in 1,6-dioxa-2,5disilepanes 2a−g considerably affects the yield and reaction rate. The time of reduction increases with an increase in the size of the spiro-fused cycloalkane ring. Thus, the reactions of peroxides with alicycles C5−C6 were brought to completion in 5−8 h, whereas reduction of peroxide containing the C12 ring demanded 9 h. It should be emphasized that, under the optimized conditions, peroxide 1d, which was produced from a gem-bishydroperoxide (1,1-bis(hydroperoxy)-4-tert-butylcyclohexane) and bis(dimethylchlorosilyl)ethane, can be selectively reduced to 2d in good yield without isolation (Table 2, footnote b). Therefore, the method described above can be employed in the direct transformation of gem-bis-hydroperoxides into Si ethers of gem-diols. Establishment of the Structures of 1,6-Dioxa-2,5disilepanes 2a−g. 1,6-Dioxa-2,5-disilepanes 2a−g are oily liquids. The structures of 2a−g were established by 1H, 13C,

It was found that triphenylphosphine (Ph3P) most selectively reduces the SiOOC group in peroxide 1d to SiOC. The best results were obtained using Et2O as the solvent. In this case, the yield of product 2d was 73%. Solvents such as THF and CH2Cl2 proved to be less efficient; the yields of product 2d obtained were 58% and trace amounts, respectively. The reduction with Ph3P at 20−25 °C requires at least 8 h for complete conversion. The reaction with triisopropyl phosphite ((PriO)3P) as the reducing agent did not lead to the complete conversion of peroxide 1d into product 2d in 8 h. The reaction with tributylphosphine (Bu3P) gave 4-tertbutylcyclohexanone as a byproduct. In the presence of thiourea, no conversion of peroxide 1d was observed within 8 h, whereas the starting substrate 1d was completely transformed into 41668


Article

Organometallics and 29Si NMR spectroscopy and elemental analysis and for compound 2d by 2D 1H,29Si HMBC experiments. In the 13C NMR spectra, characteristic signals of the OCO carbon atoms of seven-membered rings provide the most useful information; the chemical shifts of these signals (99.3−108.6 ppm) are close to those for the bis-peroxide OOCOO groups of the starting nine-membered rings (105.0−121.2 ppm). The signals of the CH3 and CH2 groups at the silicon atom are also characteristic. In the 13C NMR spectra of 1a−g, the chemical shifts of CH3 and CH2 groups are in the regions −3.5 to −3.9 ppm and 4.6 to 5.0 ppm, respectively; for 2a−g, these shifts are in the regions −0.2 to −0.4 ppm and 10.6 to 10.8 ppm, respectively. The 29Si NMR spectra also provide useful information. Thus, the 29Si chemical shifts of compounds 1a−g are in the range 25.9−26.8 ppm, whereas the shifts for reduction products 2a−g are in the range 13.6−15.3 ppm.21 Since 1,6-dioxa-2,5-disilepanes 2a−g have been previously unknown, the formation of dimeric and oligomeric (linear) products would be suggested. To the best of our knowledge, only one work has described similar seven-membered siliconcontaining acetal rings with two oxygen and two silicon atoms.22 The 2D 1H DOSY NMR experiment for 2d in the presence of internal calibrants (benzene and dibenzo-18-crown6) using a procedure developed by us confirmed the formation of the seven-membered monomeric product rather than possible oligomeric products.21 Reduction of Six-Membered Cyclic Si Peroxide to Four- and Eight-Membered Cyclic Si Ethers of gemDiols. The optimized conditions for the synthesis of 2a−g were applied to the reduction of six-membered Si gem-peroxide 3. The synthesis of 3 from gem-bis-hydroperoxide and diethyldichlorosilane and the subsequent reduction were performed without the isolation of peroxide 3 because, as demonstrated previously, this compound exists only in solution (Scheme 2).20

As opposed to the reduction of nine-membered Si peroxides 1a−d, this reaction resulted not only in ring contraction to give the four-membered Si ether 4 but also in ring expansion to give the dimeric eight-membered cyclic Si ether 5. This is the first example of the selective reduction of SiOOC to the SiOC moiety accompanied by cyclodimerization. On the basis of the literature data various reaction mechanisms can be proposed. Two of them are more probable. In accordance with the route I Ph3P attacks the oxygen atom near a carbon atom and then after reallocation of electron density and elimination of Ph3PO monoreduced product A is obtained.23 Another mechanism, II, supposes that the phosphorus atom of Ph3P is introduced between two oxygen atoms, and then after reallocation of electron density and elimination of Ph3PO, in which the oxygen atom was previously attached to a silicon atom, monoreduced product A is obtained.16e,i,24 Then, in similar ways product A is reduced to the target four-membered cycle 4. Cyclodimerization product 5 is prepared in the reaction mixture via intermediate B. It can be supposed that the components of the reaction mixture can catalyze cyclodimerization, because after isolation of 4 and 5 mixture their ratio was not changed. Base-catalyzed rearrangements of cyclosiloxanes and cyclosiloxane−polycyclosiloxane equilibrium are known.25 The structures of Si cyclic compounds 4 and 5 were determined by 1H, 13C, and 29Si NMR spectroscopy and by diffusion-ordered NMR spectroscopy (DOSY). The cyclic skeleton of the molecules was determined by applying several 1D NMR techniques. The molecular weight of the reduction products of Si peroxide 3 was estimated by DOSY. On the basis of the results of the 2D 1H DOSY technique, the formation of either one of the products (4 or 5) or a mixture of these products (4 and 5) cannot be concluded with certainty because of the overlap of the signals of products 4 and 5. Nevertheless, 3D 1H,29Si HMBC-DOSY NMR21 allowed us, due to the addition of a third dimension (29Si), to separate the overlapping signals of 4 and 5 in the 2D 1H DOSY NMR spectrum and reliably confirm the structures of products 4 and 5. Two groups of signals corresponding to different diffusion coefficients can be unambiguously attributed to monomeric product 4 and dimeric product 5 (Figure 1). The total yield of products 4 and 5 with respect to the isolated product was 67%; the 4:5 molar ratio was 1:1. In CDCl3 and in CDCl3 supplemented with nanosized silica gel, products 4 and 5 are stable for several days on storage below 0 °C. The structure of dimeric Si ether 5 was confirmed by singlecrystal X-ray diffraction (Figure 2, CCDC 1447195).

Scheme 2. Synthesis and Reduction of 9-tert-Butyl-3,3diethyl-1,2,4,5-tetraoxa-3-siladispiro[5.5]undecane (3) to Four (4)- and Eight-Membered (5) Cyclic Si Ethers of gemDiols

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CONCLUSION The reduction of 1,2,7,8-tetraoxa-3,6-disilonanes 1a−g results in the transformation of two SiOOC moieties into SiOC groups; the ring size decreases from nine to seven membered to form previously unknown 1,6-dioxa-2,5-disilepanes 2a−g. As a result, silyl ethers of gem-diols, which do not exist in the free form, were obtained. The seven-membered rings thus produced are stable under ambient conditions. They were isolated by chromatography. The yields of these compounds vary from 47 to 73%. The reduction of six-membered cyclic peroxide 3 leads not only to ring contraction giving the four-membered product 4 but also to ring expansion to yield the dimeric eightmembered cyclic product 5. 1669


Article

Organometallics

10−30 min. The Bruker TopSpin software was used for the 3D DOSY spectral processing by monoexponential fitting to the peak volume. Compound 1d and 1,2,7,8,10,11-hexaoxa-3,6-disilacyclododecane (19,19,22,22-tetramethyl-8,9,17,18,23,24-hexaoxa-19,22-disiladispiro[6.2.6.8]tetracosane) were applied as the external and internal calibrants of the molecular weight in DOSY spectra in an ∼1:1 molar ratio to the investigated substances.21 High-resolution mass spectra (HRMS) were detected using electrospray ionization (ESI).28 HRMS were measured in the positive ion mode (capillary voltage of interface 4500 V), with an m/z mass range from 50 to 3000 Da and internal/external calibration carried out with Electrospray Calibrant Solution. The flow rate of a syringe injection for solutions in MeCN was 3 μL/min. The temperature of the interface was 180 °C, and dry nitrogen gas was used. Standard silica gel plates were applied for the TLC analysis. A Kofler hot-stage apparatus was used for the melting point determinationa. Silica gel (5−40 μm, 63−200 mesh) was applied for column chromatography. Ethyl acetate (EA), CH2Cl2, Et2O, petroleum ether (PE; 40/70), H2O2 (37% aqueous solution), cyclic ketones, 4-methyl-2-pentanone, pyridine, imidazole, and diethyldichlorosilane were purchased from Acros. A diethyl ether solution of H2O2 (5.8% weight) was prepared by the extraction of Et2O (5 × 100 mL) from a solution of H2O2 (37%, 100 mL); combined ethereal extracts were dried over MgSO4. Peroxides 1a−g21 and 1,1-bis(hydroperoxy)-tert-butylcyclohexane29 were synthesized in accordance with the literature. Experiment for Table 1: Influence of the Reducing Agent and the Solvent on the Yield of 1,6-Dioxa-2,5-disilepane 2d Prepared by the Reduction of 1,2,7,8-Tetraoxa-3,6-disilonane 1d. Procedure a. A solution of the reducing agent (0.101−0.351 g, 1.34 mmol) in Et2O (1−3.5 mL) was added to a stirred solution of tetraoxadisilonane 1d (0.221 g, 0.638 mmol) in Et2O (2 mL) over 2−3 min at 20−25 °C. The stirring was continued for 8 h. In the case of Ph3P, a H2O2 solution in Et2O (∼1.4 mmol) was added to the stirred reaction mixture at 20−25 °C over 1 min, and the mixture was stirred for 5−10 min until the complete oxidation of Ph3P to Ph3PO (TLC monitoring). PE (20 mL) was added, and the mixture was passed through silica gel (1.5−2 cm, 5−40 μm) using a water-jet aspirator. Product 2d was isolated by evaporation of the solvent under vacuum (10−15 mmHg). Procedure b. A solution of Ph3P (0.351 g, 1.34 mmol) in THF (3.5 mL) was added to a solution of tetraoxadisilonane 1d (0.176−0.239 g, 0.638 mmol) in THF (2 mL) with stirring at 20−25 °C over 2−3 min. The stirring was continued for 8 h. The isolation of 2d was performed as described in Procedure a. Procedure c. A solution of Ph3P (0.351 g, 1.34 mmol) in CH2Cl2 (3.5 mL) was added to a solution of tetraoxadisilonane 1d (0.176− 0.239 g, 0.638 mmol) in CH2Cl2 (2 mL) with stirring at 20−25 °C over 2−3 min. The stirring was continued for 8 h. The isolation of 2d was performed as described in Procedure a. Experiment for Table 2: Synthesis of 1,6-Dioxa-2,5disilepanes 2a−g by the Reduction of 1,2,7,8-Tetraoxa-3,6disilonanes 1a−g with Ph3P. Procedure a: General Procedure for the Synthesis of 2a−g from 1a−g. A solution of Ph3P (0.351 g, 1.34 mmol) in Et2O (3.5 mL) was added to a solution of tetraoxadisilonane 1a−g (0.176−0.239 g, 0.638 mmol) in Et2O (2 mL) with stirring at 20−25 °C over 2−3 min. The stirring was continued for 5−9 h. Then a solution of H2O2 in Et2O (∼1.4 mmol) was added to the stirred reaction mixture at 20−25 °C over 1 min in order to oxidize Ph3P. The stirring was continued for 5−10 min until Ph3P was completely oxidized (TLC monitoring). PE (20 mL) was added, and the mixture was passed through silica gel (1.5−2 cm, 5−40 μm) using a water-jet aspirator. Products 2a−g were isolated by evaporation of the solvent under vacuum (10−15 mmHg). Procedure b. A solution of bis(dimethylchlorosilyl)ethane (0.137 g, 0.638 mmol) in Et2O (1.5 mL) was added to a stirred solution of gembis-hydroperoxide (1,1-bis(hydroperoxy)-4-tert-butylcyclohexane; 0.130 g, 0.638 mmol) and imidazole (0.091 g, 1.34 mmol, molar ratio 2.1:1 of gem-bis-hydroperoxide) in Et2O (4 mL) at 20−25 °C over 2−3 min, and then the stirring was continued for 1.5 h. To the

Figure 1. 3D 1H, 29Si HMBC-DOSY NMR spectrum of monomeric 4 and dimeric 5 Si ethers of gem-diols.

Figure 2. Molecular structure of cyclic Si acetal 5.

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EXPERIMENTAL SECTION

General Considerations. Caution! Contact of peroxides with salts of transition metals, shaking, and heating should be avoided. NMR spectra were obtained on 400 MHz (400.1 MHz, 1H; 100.6 MHz, 13C) and 300 MHz (300.1 MHz, 1H; 75.5 MHz, 13C) spectrometers in CDCl3 containing 0.05% Me4Si as the internal standard. A 300 MHz spectrometer was applied for 29Si NMR (59.6 MHz, 29Si; 300.1 MHz, 1H) spectra registration using the INEPT sequence in CDCl3 solution and Me4Si as the standard. 2D HMBC spectra were registered for the assignments of 29Si NMR signals where necessary. In some cases 29Si NMR spectral shifts were taken from the corresponding 2D spectra because of the impossibility of direct detection. 2D 1H DOSY NMR spectroscopy (diffusion-ordered spectroscopy)26 was used for determination of the diffusion coefficients in CDCl3 solutions on a 300 MHz spectrometer (300.1 MHz, 1H). The parameters Δ = 100 ms and Te = 5 ms were applied for the BPP-LED pulse sequence. The SCORE algorithm using the BrukerTopSpin and DOSYToolbox software and monoexponential fitting were used for the 2D DOSY spectral processing.27 Dibenzo-18crown-6, 1,2,7,8-tetraoxa-3,6-disilonane (3-tert-butyl-9,9,12,12-tetramethyl-7,8,13,14-tetraoxa-9,12-disilaspiro[5.8]tetradecane; 1d), and 1,2,7,8,10,11-hexaoxa-3,6-disilacyclododecane (19,19,22,22-tetramethyl-8,9,17,18,23,24-hexaoxa-19,22-disiladispiro[6.2.6.8]tetracosane)21 were used as the internal and external calibrants of the molecular weight in DOSY spectra in an ∼1:1 molar ratio to the studied compounds. 3D 1H,29Si DOSY-HMBC NMR spectra were registered in CDCl3 on a 300 MHz spectrometer (300.1 MHz, 1H). A combination of HMBC and BBP-LED sequences was used with Δ = 100 ms, Te = 5 ms, and JSiH = 6 Hz. The period of an experiment was 1670


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Organometallics

continued for 1 h, and then a solution of H2O2 in Et2O (∼1.4 mmol) was added with stirring at 20−25 °C in order to oxidize Ph3P. The reaction mixture was stirred for 5−10 min until Ph3P was completely oxidized (TLC monitoring). PE (20 mL) was added, and the mixture was passed through silica gel (1.5−2 cm, 5−40 μm) using a water-jet aspirator. A mixture of products 4 and 5 was obtained by solvent evaporation under vacuum (10−15 mmHg). 7-tert-Butyl-2,2-diethyl-1,3-dioxa-2-siladispiro[3.5]nonane (4) and 3,13-Di-tert-butyl-8,8,17,17-tetraethyl-7,9,16,18-tetraoxa-8,17disiladispiro[5.3.5.3]octadecane (5). The 4:5 ratio was determined on the basis of the ratio of the integrated intensities in the 1H NMR spectrum (4:5 ≈ 1:1). Oil. Rf = 0.77 (TLC, hexane/EA, 10/1). 1H NMR (300.13 MHz, CDCl3): δ 0.6−0.7 (m, 4H, 8H), 0.8−0.9 (m, 9H, 18H), 0.95−1.05 (m, 6H, 12H), 1.2−2.05 (m, 9H, 18H). 13C NMR (75.48 MHz, CDCl3): δ 6.27, 6.65, 6.92, 7.62, 7.75, 24.28, 24.27, 27.77, 32.36, 32.39, 41.00, 41.69, 47.19, 47.32. 29Si NMR (59.6 MHz, CDCl3): δ −7.16, −13.55. Anal. Calcd for C14H28O2Si, C28H56O4Si2: C, 65.57; H, 11.00; Si, 10.95. Found: C, 65.61; H, 11.03; Si, 10.92 Analysis of Products 4 and 5 using 2D 1H DOSY NMR. A 4/5 mixture (1/1; 53.4 mg) and calibrants dibenzo-18-crown-6 (25.0 mg, 0.0694 mmol) and benzene (5.4 mg, 0.0694 mmol) were dissolved in CDCl3 (0.6 mL) in a NMR tube, and then nanosized silica gel (1 wt %) was added and the tube was shaken. The 2D 1H DOSY NMR spectrum was registered. Analysis of Products 4 and 5 using 3D 1H,29Si HMBC-DOSY NMR (Figure 1). A 4/5 mixture (1/1) (36.0 mg) was dissolved in CDCl3 (0.6 mL) in a NMR tube, and then nanosized silica gel (1 wt %) was added and the tube was shaken. The 3D 1H, 29Si DOSY-HMBC NMR spectrum was registered. Synthesis of Peroxide 3 and Its Analysis using 1H, 29Si, and HMBC NMR. gem-Bis-hydroperoxide (1,1-bis(hydroperoxy)-4-tertbutylcyclohexane; 35.2 mg, 0.1724 mmol) and pyridine (28.6 mg, 0.362 mmol) in a molar ratio of 1:2.1 were placed in an NMR tube and dissolved in CDCl3 (0.6 mL). The tube was purged with argon, and then diethyldichlorosilane (27.1 mg, 0.1724 mmol) was added. After storage for 1 h, 1H, 29Si, and HMBC NMR spectra were registered. Synthesis of Peroxide 3 and Its Analysis using 2D 1H DOSY NMR. gem-Bis-hydroperoxide (1,1-bis(hydroperoxy)-4-tert-butylcyclohexane; 35.2 mg, 0.1724 mmol) and pyridine (28.6 mg, 0.362 mmol) in a molar ratio of 1:2.1 were placed in the NMR tube and dissolved in CDCl3 (0.6 mL). The tube was purged with argon, and then diethyldichlorosilane (27.1 mg, 0.1724 mmol) was added; after 1 h, dibenzo-18-crown-6 (25.0 mg, 0.0694 mmol) was added as a calibrant. After that, nanosized silica gel (1 wt %) was loaded, and the NMR tube was shaken. The 2D 1H DOSY NMR spectrum was registered.

stirred reaction mixture was added a solution of Ph3P (0.351 g, 1.34 mmol) in Et2O (3.5 mL) over 2−3 min at 20−25 °C, and then the stirring was continued for 8 h. The isolation of 2d was performed as described in Procedure a. 7,7,10,10-Tetramethyl-6,11-dioxa-7,10-disilaspiro[4.6]undecane (2a). Oil. Rf = 0.57 (TLC, hexane/EA, 10/1). 1H NMR (300.13 MHz, CDCl3): δ 0.12 (s, 12H), 0.73 (s, 4H), 1.58−1.80 (m, 8H) .13C NMR (75.48 MHz, CDCl3): δ −0.19, 10.69, 22.73, 41.79, 108.57. 29Si NMR (59.6 MHz, CDCl3): δ 15.25. Anal. Calcd for C11H24O2Si2: C, 54.04; H, 9.89; Si, 22.98. Found: C, 54.10; H, 9.91; Si, 22.94. 8,8,11,11-Tetramethyl-7,12-dioxa-8,11-disilaspiro[5.6]dodecane (2b). Oil. Rf = 0.79 (TLC, hexane/EA, 10/1). 1H NMR (300.13 MHz, CDCl3): δ 0.13 (s, 12H), 0.74 (s, 4H), 1.26−1.65 (m, 10H). 13C NMR (75.48 MHz, CDCl3): δ 0.32, 10.69, 23.83, 25.46, 41.02, 99.37. 29Si NMR (59.6 MHz, CDCl3): δ 13.65. Anal. Calcd for C12H26O2Si2: C, 55.75; H, 10.14; Si, 21.73. Found: C, 55.78; H, 10.13; Si, 21.76. 3,8,8,11,11-Pentamethyl-7,12-dioxa-8,11-disilaspiro[5.5]dodecane (2c). Oil. Rf = 0.68 (TLC, hexane/EA, 10/1). 1H NMR (300.13 MHz, CDCl3): δ 0.07−16 (m, 12H), 0.70−0.75 (m, 4H), 0.85−1.83 (m, 12H). 13C NMR (75.48 MHz, CDCl3): δ 0.23, 0.39, 10.63, 10.75, 21.78, 31.58, 32.24, 40.37, 99.33. 29Si NMR (59.6 MHz, CDCl3): δ 13.53, 13.91. Anal. Calcd for C13H28O2Si2: C, 57.29; H, 10.36; Si, 20.61. Found: C, 57.34; H, 10.37; Si, 20.62. 3-tert-Butyl-8,8,11,11-tetramethyl-7,12-dioxa-8,11-disilaspiro[5.6]dodecane (2d). Oil. Rf = 0.81 (TLC, hexane/EA, 10/1). 1H NMR (300.13 MHz, CDCl3): δ 0.10−0.15 (m, 12H), 0.72−0.75 (m, 4H), 0.83 (s, 9H), 0.88−1.87 (m, 9H). 13C NMR (75.48 MHz, CDCl3): δ 0.2, 0.35, 10.61, 10.82, 24.48, 27.64, 30.23, 40.91, 47.11, 99.34. 29Si NMR (59.6 MHz, CDCl3): δ 13.58. Anal. Calcd for C16H34O2Si2: C, 61.08; H, 10.89; Si, 17.85. Found: C, 61.13; H, 10.91; Si, 17.89. HRMS (ESI) m/z [M + Na]+ calcd for [C16H32O6Si2]+ 399.1630, found 399.1629. Analysis of 3-tert-Butyl-8,8,11,11-tetramethyl-7,12-dioxa-8,11disilaspiro[5.6]dodecane (2d) using 2D 1H DOSY NMR. Compound 22d (22.0 mg, 0.0694 mmol) and calibrants dibenzo-18-crown-6 (25.0 mg, 0.0694 mmol) and benzene (5.4 mg, 0.0694) were dissolved in CDCl3 (0.6 mL) in a NMR tube, and then nanosized silica gel (1 wt %) was loaded and the tube was shaken. The 2D 1H DOSY NMR spectrum was registered. 2,2,4,8,8,11,11-Heptamethyl-7,12-dioxa-8,11-disilaspiro[5.6]dodecane (2e). Oil. Rf = 0.57 (TLC, hexane/EA, 10/1). 1H NMR (300.13 MHz, CDCl3): δ 0.10−0.20 (m, 12H), 0.69−1.9 (m, 20H). 13 C NMR (75.48 MHz, CDCl3), δ 0.21, 0.35, 0.39, 0.44, 10.64, 10.87, 22.12, 26.20, 26.46, 29.72, 32.03, 34.09, 48.23, 49.59, 52.05, 100.29. 29 Si NMR (59.6 MHz, CDCl3): δ 13.03, 14.17. Anal. Calcd for C15H32O2Si2: C, 59.94; H, 10.73; Si, 18.69. Found: C, 59.86; H, 10.71; Si, 18.72. 2,2,5,5-Tetramethyl-1,6-dioxa-2,5-disilaspiro[6.6]tridecane (2f). Oil. Rf = 0.77 (TLC, hexane/EA, 10/1). 1H NMR (300.13 MHz, CDCl3): δ 0.14 (s, 12H), 0.76 (s, 4H), 1.40−1.87 (m, 12H). 13C NMR (75.48 MHz, CDCl3): δ 0.35, 10.69, 22.07, 28.27, 44.51, 103.05. 29Si NMR (59.6 MHz, CDCl3): δ 13.17. Anal. Calcd for C13H28O2Si2:C, 57.29; H, 10.36; Si, 20.61. Found: C, 57.21; H, 10.38; Si, 20.63. 2,2,5,5-Tetramethyl-1,6-dioxa-2,5-disilaspiro[6.11]octadecane (2g). White crystals. Mp: 86−89 °C (CH2Cl2). Rf = 0.9 (TLC, hexane/EA, 10/1). 1H NMR (300.13 MHz, CDCl3): δ 0.14 (s, 12H), 0.73 (s, 4H), 1.24−1.76 (m, 22H). 13C NMR (75.48 MHz, CDCl3): δ 0.04, 10.82, 20.73, 22.29, 22.55, 26.06, 26.23, 29.70, 37.34, 102.92. 29Si NMR (59.6 MHz, CDCl3): δ 13.59. Anal. Calcd for C18H38O2Si2: C, 63.09; H, 11.18; Si, 16.39. Found: C, 63.15; H, 11.21; Si, 16.45. Synthesis and Reduction of 9-tert-Butyl-3,3-diethyl-1,2,4,5tetraoxa-3-siladispiro[5.5]undecane (3) to Four (4)- and EightMembered (5) Cyclic Si Ethers of gem-Diols. A solution of diethyldichlorosilane (84.0 mg, 0.535 mmol) in Et2O (2 mL) was added to a vigorously stirred solution of gem-bis-hydroperoxide (1,1bis(hydroperoxy)-4-tert-butylcyclohexane; 109 mg, 0.535 mmol) and imidazole (76.0 mg, 1.123 mmol, molar ratio 2.1:1 of gem-bishydroperoxide) in Et2O (4 mL) at 20−25 °C over 2−3 min, and then the stirring was continued for 1 h. A solution of Ph3P (295 mg, 1.123 mmol) in Et2O (3 mL) was added to the stirred reaction mixture containing peroxide 3 at 25 °C over 2−3 min, the stirring was

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.6b00129. 1 H, 13C, and 29Si NMR spectra for 2a−g and 3−5, 2D 1 29 H, Si HMBC NMR spectrum for 2d and 3−5, 2D 1H DOSY NMR spectra for 2d and 3−5, 3D 1H,29Si HMBC-DOSY NMR spectra for 4 and 5, and X-ray diffraction data for compound 5 (PDF) X-ray diffraction data for compound 5 (CIF)

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AUTHOR INFORMATION

Corresponding Author

*A.O.T.: e-mail, [email protected]; fax, +7 499 135 53 28. Notes

The authors declare no competing financial interest. 1671


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ACKNOWLEDGMENTS This work was supported by the Russian Science Foundation (Grant No. 14-23-00150).

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