1-Phenyl-1-X-1-silacyclohexanes (X = MeO, OH, Me2N)

Suslova, E. N.; Shainyan, B. А.

doi:10.1134/s1070363217070349

Cited by 5 publications

(7 citation statements)

References 16 publications

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“…Reactions were generally performed in flame-dried glassware under argon atmosphere. Compounds 1 , 2 and 5 were prepared according to reported procedures. , Analytical thin layer chromatography was performed on silica gel 60 F254 aluminum plates (visualization with iodine vapors). Column chromatography was performed on silica Geduran Si 60 (0.063–0.200 mm, Merck) using the indicated solvents.…”

Section: Methodsmentioning

confidence: 99%

“…As to geminally substituted 1-X-1-phenylsilacyclohexanes having an electron acceptor group X, a series of such compounds [X = F, Cl, Br, MeO, OH, Me 2 N, OSi(Ph)C 5 H 10 ] was synthesized by us recently 9 and the first two (X = F, Cl) were studied conformationally. 10 In solution, the ratio of the conformers Ph eq :Ph ax is ∼3:1 for X = F and ∼4.5:1 for X = Cl.…”

Section: ■ Introductionmentioning

confidence: 99%

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Conformational Preferences of the Phenyl Group in 1-Phenyl-1-X-1-silacyclo-hexanes (X = MeO, HO) and 3-Phenyl-3-X-3-silatetrahydropyrans (X = HO, H) by Low Temperature ¹³C NMR Spectroscopy and Theoretical Calculations

2017

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New Si-phenyl-substituted silacyclohexanes and 3-silatetrahydropyrans have been synthesized and studied with respect to the conformational equilibria of the heterosix-membered ring by low temperature C NMR spectroscopy and quantum chemical calculations. For 1-methoxy-1-phenylsilacyclohexane 1 and 3-phenyl-3-silatetrahydropyran 4 the conformational equilibria could be frozen and assigned. The Ph ⇆ Ph equilibrium constants at 103 K are 2.21 for 1 and 4.59 for 4. In complete agreement with former studies of similar silicon compounds, molecules 1 and 4 prefer to adopt the Ph conformation. The conformational equilibria of 1-hydroxy-1-phenylsilacyclohexane 2 and 3-hydroxy-3-phenyl-3-silatetrahydropyran 3 could not be frozen at 100 K and proved to be heavily one-sided (if not anancomeric). Obviously, there is a general trend of predominance of Ph conformer in the gas phase and of Ph in solution. For the isolated molecules of silanols 2 and 3, calculations allowed to explain the axial predominance of the phenyl group by a larger polarization of the Si-Ph than of the Si-O bond in the Ph conformer and additional destabilization of 3-Ph conformer by repulsion of unidirectional dipoles of the endocyclic oxygen lone pair and of the highly polar axial Si-O bond.

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Section: Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Conformational Preferences of the Phenyl Group in 1-Phenyl-1-X-1-silacyclo-hexanes (X = MeO, HO) and 3-Phenyl-3-X-3-silatetrahydropyrans (X = HO, H) by Low Temperature ¹³C NMR Spectroscopy and Theoretical Calculations

2017

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“…Our recent studies [72], [83] on 1-hydroxy-1-phenyl-and 1-methoxy-1-phenylsilacyclohexane, synthesized as described in [84], allow one to compare the gas vs. solution conformational preference of these compounds. Unfortunately, no decoalescence of the 13 C signals could be reached for 1-hydroxy-1-phenylsilacyclohexane in solution, but for 1-methoxy-1-phenylsilacyclohexane a significant predominance of the Ph eq conformer (Ph ax :Ph eq = 31.2:68.8) was measured at 103 K [72].…”

Section: Solution Vs Gas Conformational Preferences In Miscellaneousmentioning

confidence: 99%

“…The compound was synthesized in 56% yield as shown in Scheme 2. The compound is rather unstable and is gradually hydrolyzed with time to siloxane with the rupture of the Si-N bond [84]. Pheq in solution is anticipated being in compliance with all rules governing the conformational preferences, the gas phase measurements are unexpected and extremely surprising.…”

Section: Miscellaneous Silacyclohexanes and Related Compoundsmentioning

confidence: 99%

“…The compound was synthesized in 56% yield as shown in Scheme 2. The compound is rather unstable and is gradually hydrolyzed with time to siloxane with the rupture of the Si-N bond [84]. The conformational equilibrium of 1-(Me2N)-1-Ph-1-silacyclohexane was studied by GED, 13 C LT NMR and theoretical calculations [85].…”

Section: Miscellaneous Silacyclohexanes and Related Compoundsmentioning

confidence: 99%

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Silacyclohexanes, Sila(hetero)cyclohexanes and Related Compounds: Structure and Conformational Analysis

Shainyan

2020

Molecules

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Conformational analysis of Si-mono- and Si,Si-disubstituted silacyclohexanes as well as their analogues with a heteroatom(s) in the ring is reviewed with the focus on the recent results. Experimental measurements in the gas phase (gas electron diffraction, GED) and low temperature NMR spectroscopy (LT NMR) on 1H, 13C and 29Si nuclei are described along with theoretical calculations at the DFT and MP2 levels of theory. Structural and conformational specific features are shown to be principally different from those of the carbon predecessors—the corresponding cyclohexanes, oxanes, thianes and piperidines. The role of various effects (steric, hyperconjugation, stereoelectronic, electrostatic) is demonstrated.

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1-t-Butyl-1-phenyl-1-silacyclohexane: Synthesis, conformational analysis in gas and solution by GED, FT-IR and theoretical calculations

Shainyan

Suslova

Phien

et al. 2020

Journal of Organometallic Chemistry

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1-Phenyl-1-X-1-silacyclohexanes (X = MeO, OH, Me2N)

Cited by 5 publications

References 16 publications

Conformational Preferences of the Phenyl Group in 1-Phenyl-1-X-1-silacyclo-hexanes (X = MeO, HO) and 3-Phenyl-3-X-3-silatetrahydropyrans (X = HO, H) by Low Temperature ¹³C NMR Spectroscopy and Theoretical Calculations

Conformational Preferences of the Phenyl Group in 1-Phenyl-1-X-1-silacyclo-hexanes (X = MeO, HO) and 3-Phenyl-3-X-3-silatetrahydropyrans (X = HO, H) by Low Temperature ¹³C NMR Spectroscopy and Theoretical Calculations

Silacyclohexanes, Sila(hetero)cyclohexanes and Related Compounds: Structure and Conformational Analysis

1-t-Butyl-1-phenyl-1-silacyclohexane: Synthesis, conformational analysis in gas and solution by GED, FT-IR and theoretical calculations

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1-Phenyl-1-X-1-silacyclohexanes (X = MeO, OH, Me2N)

Cited by 5 publications

References 16 publications

Conformational Preferences of the Phenyl Group in 1-Phenyl-1-X-1-silacyclo-hexanes (X = MeO, HO) and 3-Phenyl-3-X-3-silatetrahydropyrans (X = HO, H) by Low Temperature 13C NMR Spectroscopy and Theoretical Calculations

Conformational Preferences of the Phenyl Group in 1-Phenyl-1-X-1-silacyclo-hexanes (X = MeO, HO) and 3-Phenyl-3-X-3-silatetrahydropyrans (X = HO, H) by Low Temperature 13C NMR Spectroscopy and Theoretical Calculations

Silacyclohexanes, Sila(hetero)cyclohexanes and Related Compounds: Structure and Conformational Analysis

1-t-Butyl-1-phenyl-1-silacyclohexane: Synthesis, conformational analysis in gas and solution by GED, FT-IR and theoretical calculations

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Product

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Conformational Preferences of the Phenyl Group in 1-Phenyl-1-X-1-silacyclo-hexanes (X = MeO, HO) and 3-Phenyl-3-X-3-silatetrahydropyrans (X = HO, H) by Low Temperature ¹³C NMR Spectroscopy and Theoretical Calculations

Conformational Preferences of the Phenyl Group in 1-Phenyl-1-X-1-silacyclo-hexanes (X = MeO, HO) and 3-Phenyl-3-X-3-silatetrahydropyrans (X = HO, H) by Low Temperature ¹³C NMR Spectroscopy and Theoretical Calculations