α- et β-silacyclopentanols

doi:10.1016/S0022-328X(00)82591-7

Journal of Organometallic Chemistry

Volume 30, Issue 1, 1 July 1971, Pages 5-19

https://doi.org/10.1016/S0022-328X(00)82591-7 Get rights and content

Abstract

1,1-Dimethyl-1-silacyclopentan-3-ols are synthetised by hydroboration—oxidation or epoxidation—reduction of the corresponding silacyclopent-3-enes. In acidic media, β-silacyclopentanols give ring opening reactions. Secondary sila-β-alcohols are rearranged by Raney nickel on warming to give 1-oxa-2-sila-cyclopentanes. Thermal dehydration of tertiary β-alcohols gives a mixture of cyclenic isomers from which α-silacyclopentanols can be prepared.

Silacyclopentane-3,4-diols are obtainable from the acidic cleavage of the epoxidic ring of oxasilabicyclohexanes.

Résumé

Nous avons obtenu les diméthyl-1,1 silacyclopentanols-3 à partir des silacyclopentènes-3 correspondants soit par hydroboration—oxydation, soit par époxydation—réduction de la double liaison éthylénique intracyclique. Les β-silacyclopentanols ainsi préparés donnent lieu en milieu acide, à des réactions d'ouverture de cycle. Traités à chaud par le nickel de Ranay, les β-alcools secondaires siliciés se transposent en oxa-1 sila-2 cyclopentanes. La déshydratation thermique des β-alcools tertiaires conduit à un mélange d'isomères cycléniques, à partir duquel il est possible d'accéder aux α-silacyclopentanols. L'ouverture acide des oxasilabicyclohexanes conduit aux silacyclopentanediols-3,4.

Références (37)

J. Dunogues et al.
J. Organometal. Chem.
(1970)
G. Manuel et al.
J. Organometal. Chem.
(1969)
M. Massol et al.
J. Organometal. Chem.
(1970)
I.F. Lutsenko et al.
J. Organometal. Chem.
(1968)
D.R. Weyenberg et al.
J. Org. Chem.
(1968)
O.M. Nefedov et al.
Izv. Akad. Nauk. SSSR, Ser. Khim.
(1964)
A. Valette
Justus Liebigs Ann. Chem.
(1948)
H.C. Brown et al.
J. Amer. Chem. Soc.
(1961)
P. Mazerolles et al.
C.R. Acad. Sci.
(1968)
M. Vilkas
Bull. Soc. Chim. Fr.
(1959)

L.W. Trevoy et al.

J. Amer. Chem. Soc.

(1949)

R.A. Miller

(1957)

P. Mazerolles et al.

C.R. Acad. Sci.

(1968)

W.H. Knoth et al.

J. Amer. Chem. Soc.

(1958)

J.L. Speier et al.

J. Org. Chem.

(1960)

G. Rossmy et al.

Makromol. Chem.

(1964)

K.A. Andrianov et al.

Dokl. Akad. Nauk. SSSR

(1963)

W. Simmler et al.

Chem. Ber.

(1966)

Cited by (42)

Unprecedented effects of the trimethylsilyl group on the reactivity of 3C-silylated silacyclopentenes and their derivatives
2000, Journal of Organometallic Chemistry
We have synthesised new 3C-silylated silacyclopentenes from the corresponding 3-trimethylsilyl-1,1-dichloro-1-silacyclopent-3-enes. The presence of two metal centres M (M=Si) in α and β-positions confers an original structure for these new heterocycles. The chemical behaviour of such compounds and their derivatives was studied and compared to the results obtained in the non-substituted silacyclopentane series.
Synthèses de 3-silyl et de 3-germyl 1-sila et 1-germacyclopent-3-ènes
1993, Journal of Organometallic Chemistry
The synthesis of allylic sila (and germa) cyclopentenes containing an Et₃M (M  Si, Ge) group in vinylic position is described. 1-Germacyclopent-3-enes 3-silylated (IIIa) and 3-germylated (IIIb) result from 1,4-cycloaddition of GeI₂ to the corresponding 2-metallated 1,3-dienes (II). 3-Metallated 1-silacyclopent-3-enes (IIIc–IIIf) are obtained by two methods. One involves the reaction of dienes II with Me₂SiCl₂ and Mg, leading to compounds IIIc (M  Si) and IIId (M  Ge). The other method corresponds to the trichlorosilylation (HSiCl₃, Et₃N, ϵ Cu₂Cl₂) of dichlorinated compounds I resulting from cis-addition of Et₃MH to cis-1,4-dichlorobutyne. From the two trichlorosilylated derivatives IV and V, formed in S_N2 and S_N2′ reactions, only the 1-trichlorosilyl 2-triethylsilyl (and germyl) 4-chlorobut-2-enes (IV) give, in the presence of magnesium, the 1,1-dichloro 3-triethylsilyl (and germyl) 1-silacyclopent-3-enes (IIIe and IIIf).
Nous décrivons la synthèse de sila (et germa) cyclopentènes allyliques (III) renfermant le groupe Et₃M (M  Si, Ge) en position vinylique. Les 1-germacyclopent-3-ènes 3-silylés (IIIa) et 3-germylés (IIIb) sont obtenus par réaction de cycloaddition-1,4 de GeI₂ sur les diènes 2-métallés (II) correspondants. Les 1-silacyclopent-3-ènes métallés (IIIc–IIIf) sont préparés selon deux méthodes. L'une, mettant en jeu les diènes II et le couple Me₂SiCl₂ Mg, conduit aux cycles IIIc (M  Si) et IIId (M  Ge). L'autre méthode consiste à effectuer la réaction de trichlorosilylation (HSiCl₃, Et₃N, ϵ Cu₂Cl₂) des dérivés dichlorés I qui résultent de la cis-addition de Et₃MH au cis-1,4-dichlorobutyne. Des deux dérivés trichlorosilylés IV et V formés à l'issue des réactions S_N2 et S_N2′, seuls les 1-trichlorosilyl 2-triéthylsilyl (et germyl) 4-chlorobut-2-ènes (IV) conduisent, après cyclisation par le magnésium, aux 1,1-dichloro-3-triéthylsilyl (et germyl) 1-silacyclopent-3-enes (IIIe et IIIf).
Sila et germacyclopentanes C-bifonctionnels. I. 1-Sila et 1-germacyclopentan-2,3 et 3,4-diols
1993, Journal of Organometallic Chemistry
C-bifunctional sila- and germacyclopentanes have some potential as biologically active drugs. Ten representative 1-sila (and 1-germa) cyclopentane-2,3 and 3,4-diols, cis or trans, were synthesized from the corresponding 1-metallacyclopen-3-enes. The influence of the metal, silicon or germanium, on each step leading to 3 sets of α-diols is underlined. The stereochemistry of the α-diols and their precursors was established by ¹H and ¹³C NMR spectroscope.
Les sila et germacyclopentanes C-bifonctionnels étant des précurseurs potentiels de nouveaux produits biologiquement actifs, nous avons mis au point des méthodes de synthèse de 1-sila (et 1-germa) cyclopentan-2,3 et 3,4-diols cis et trans à partir des 1-métallacyclopent-3-ènes correspondents. Nous mettons en avant le rôle du métal, silicium ou germanium, sur chacune des étapes conduisant aux 3 séries de nouveaux α-diols. La stéréochimie de ces diols et de leurs précurseurs a été établie par RMN ¹H et ¹³C.
Direct spectroscopic study of unstable molecules with siliconoxygen multiple bonds: low temperature matrix stabilization of (CH<inf>3</inf>)<inf>2</inf>SiO and (CD<inf>3</inf>)<inf>2</inf> SiO in the gas phase
1988, Journal of Organometallic Chemistry
To continue the IR spectroscopic investigations of intermediates with double-bonded silicon, the silanones (CH₃)₂SiO and (CD₃)₂SiO have been generated by vacuum pyrolysis of the corresponding 6-oxa-3-silabicyclo[3.1.0]hexanes and of DielsAlder adducts of silapyranes with maleic anhydride. The above silanones have first been stabilized from the gas phase in argon matrices at 12 K and studied by IR spectroscopy. Using the dependence of the spectra on temperature and pressure in the pyrolysis zone or in warming-up experiments (to 35–40 K) the following vibrational bands of silanones have been revealed: (CH₃)₂SiO 1244, 1240, 1210, 822, 798, 770, 657 cm⁻¹; (CD₃)₂SiO 1215, 1032, 1007, 995, 712, 685, 674 cm⁻¹. The limits of thermal (≈ 850°C) and kinetic (5 × 10⁻⁴ torr) stability of dimethylsilanone were determined. By comparison of frequencies found with computed values the band 1210 cm⁻¹ in (CH₃)₂SiO (1215 cm⁻¹ in (CD₃)₂SiO) was assigned to a SiO stretching vibration. This frequency as well as the calculated force constant (8.32 mdyn/&rA) and order (1.45) of the SiO bond are considered as evidence of significant double bonding in dimethylsilanone.
Thia-6 diphényl-3,3 sila-3 (et germa-3)bicyclo[3.1.0]hexanes
1987, Journal of Organometallic Chemistry
6-Thia-3,3-diphenyl-3-sila-(and 3-germa-)bicyclo[3.1.0]hexanes are prepared from the corresponding metallaoxiranes using triphenylphosphorus sulfide with trifluoroacetic acid as solvent. These thiiranes are unstable compared to the corresponding oxiranes. Partial desulfurization results from thermic or chemical processes leading to 1-metallacyclopent-3-enes. Cyclometallathianes are potential precursors of metallathiones and thiofunctional metallacyclopentanes.
Thermal isomerization of 3-silabicyclo[3.1.0]hexanes: A new route to silacyclopentenes and silacyclohexenes
1984, Journal of Organometallic Chemistry

View all citing articles on Scopus

View full text

α- et β-silacyclopentanols

Abstract

Résumé

J. Organometal. Chem.

J. Organometal. Chem.

J. Organometal. Chem.

J. Organometal. Chem.

J. Org. Chem.

Izv. Akad. Nauk. SSSR, Ser. Khim.

Justus Liebigs Ann. Chem.

J. Amer. Chem. Soc.

C.R. Acad. Sci.

Bull. Soc. Chim. Fr.

J. Amer. Chem. Soc.

C.R. Acad. Sci.

J. Amer. Chem. Soc.

J. Org. Chem.

Makromol. Chem.

Dokl. Akad. Nauk. SSSR

Chem. Ber.