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Special Issue "Organosilicon Chemistry"

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A special issue of Molecules (ISSN 1420-3049).

Deadline for manuscript submissions: closed (31 August 2011)

Special Issue Editor

Guest Editor
Prof. Dr. Scott Sieburth (Website)

Department of Chemistry, Temple University, 1901 N. 13th Street, Philadelphia, PA 19122, USA
Interests: synthetic organic and medicinal chemistry; organosilicon chemistry

Published Papers (4 papers)

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Research

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Open AccessArticle Lipase-Catalyzed Kinetic Resolution of Aryltrimethylsilyl Chiral Alcohols
Molecules 2011, 16(11), 9697-9713; doi:10.3390/molecules16119697
Received: 27 September 2011 / Revised: 28 October 2011 / Accepted: 17 November 2011 / Published: 23 November 2011
Cited by 4 | PDF Full-text (243 KB)
Abstract
Lipase-catalyzed kinetic resolution of aryltrimethylsilyl chiral alcohols through a transesterification reaction was studied. The optimal conditions found for the kinetic resolution of m- and p-aryltrimethylsilyl chiral alcohols, led to excellent results, high conversions (c = 50%), high enantiomeric ratios [...] Read more.
Lipase-catalyzed kinetic resolution of aryltrimethylsilyl chiral alcohols through a transesterification reaction was studied. The optimal conditions found for the kinetic resolution of m- and p-aryltrimethylsilyl chiral alcohols, led to excellent results, high conversions (c = 50%), high enantiomeric ratios (E > 200) and enantiomeric excesses for the remaining (S)-alcohol and (R)-acetylated product (>99%). However, kinetic resolution of o-aryltrimethylsilyl chiral alcohols did not occur under the same conditions applied to the other isomers. Full article
(This article belongs to the Special Issue Organosilicon Chemistry)
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Open AccessArticle Dissociation of the Disilatricyclic Diallylic Dianion [(C4Ph4SiMe)2]−2 to the Silole Anion [MeSiC4Ph4] by Halide Ion Coordination or Halide Ion Nucleophilic Substitution at the Silicon Atom
Molecules 2011, 16(10), 8451-8462; doi:10.3390/molecules16108451
Received: 26 August 2011 / Revised: 1 October 2011 / Accepted: 1 October 2011 / Published: 10 October 2011
Cited by 2 | PDF Full-text (381 KB)
Abstract
The reductive cleavage of the Si-Si bond in 1,1-bis(1-methyl-2,3,4,5-tetraphenyl-1-silacyclopentadiene) [(C4Ph4SiMe)2] (1) with either Li or Na in THF gives the silole anion [MeSiC4Ph4] (2). The head-to-tail dimerization [...] Read more.
The reductive cleavage of the Si-Si bond in 1,1-bis(1-methyl-2,3,4,5-tetraphenyl-1-silacyclopentadiene) [(C4Ph4SiMe)2] (1) with either Li or Na in THF gives the silole anion [MeSiC4Ph4] (2). The head-to-tail dimerization of the silole anion 2 gives crystals of the disilatricyclic diallylic dianion [(C4Ph4SiMe)2]−2 (3). The derivatization of 3 (crystals) with bromoethane (gas) under reduced pressure provides [(MeSiC4Ph4Et)2] (4) quantitatively. The reverse addition of 3 in THF to trimethylsilyl chloride, hydrogen chloride, and bromoethane in THF gives 1-methyl-1-trimethylsilyl-1-silole [Me3SiMeSiC4Ph4] (6), 1-methyl-2,3,4,5-tetraphenyl-1-silacyclo-3-pentenyl-1-methyl-1-silole [C4Ph4H2SiMe-MeSiC4Ph4] (7), and 1-methyl-2,5-diethyl-2,3,4,5-tetraphenyl-1-silacyclo-3-pentenyl-1-methyl-1-silole [C4Ph4Et2SiMe-MeSiC4Ph4] (8), respectively. The reaction products unambiguously suggest that the silole anion [MeSiC4Ph4] is generated by coordination of the chloride ion at the silicon atom in 3 or by the nucleophilic substitution of either chloride or bromide ion at one of two silicon atoms in 3. The quenching reaction of 3 dissolved in THF with water gives 1,2,3,4-tetraphenyl-2-butene, the disiloxane of 1-methyl-2,3,4,5-tetraphenyl-1-silacyclo-3-pentenyl [O(MeSiC4Ph4)2] (10) and methyl silicate. Full article
(This article belongs to the Special Issue Organosilicon Chemistry)
Open AccessCommunication Synthesis and NMR-Study of the 2,3,4,5-Tetraethylsilole Dianion [SiC4Et4]2−•2[Li]+
Molecules 2011, 16(9), 8033-8040; doi:10.3390/molecules16098033
Received: 31 August 2011 / Revised: 8 September 2011 / Accepted: 14 September 2011 / Published: 16 September 2011
Cited by 4 | PDF Full-text (419 KB)
Abstract
The previously unknown silole dianion [SiC4Et4]2−•2[Li]+ (3) was prepared by the sonication of 1,1-dichloro-2,3,4,5-tetraethyl-1-silacyclopentadiene [Cl2SiC4Et4, 2] with more than four equivalent of lithium in THF. 1 [...] Read more.
The previously unknown silole dianion [SiC4Et4]2−•2[Li]+ (3) was prepared by the sonication of 1,1-dichloro-2,3,4,5-tetraethyl-1-silacyclopentadiene [Cl2SiC4Et4, 2] with more than four equivalent of lithium in THF. 1H-, 13C-, and 29Si-NMR data of 3 are compared with those of the reported silole dianion [SiC4Ph4]2−. Trapping of 3 with trimethylchlorosilane gave 1,1-bis(trimethylsilyl)-2,3,4,5-tetraethyl-1-silacyclopentadiene [(Me3Si)2SiC4Et4, 4] in high yield. The silole of 2 was synthesized in high yield in three steps by a modified procedure using Cp2ZrCl2 via Cp2ZrC4Et4 and 1,4-dibromo-1,2,3,4-tetraethyl-1,3-butadiene. Full article
(This article belongs to the Special Issue Organosilicon Chemistry)

Review

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Open AccessReview Recent Applications of the (TMS)3SiH Radical-Based Reagent
Molecules 2012, 17(1), 527-555; doi:10.3390/molecules17010527
Received: 29 November 2011 / Revised: 29 December 2011 / Accepted: 2 January 2012 / Published: 6 January 2012
Cited by 26 | PDF Full-text (582 KB)
Abstract
This review article focuses on the recent applications of tris(trimethylsilyl)silane as a radical-based reagent in organic chemistry. Numerous examples of the successful use of (TMS)3SiH in radical reductions, hydrosilylation and consecutive radical reactions are given. The use of (TMS)3 [...] Read more.
This review article focuses on the recent applications of tris(trimethylsilyl)silane as a radical-based reagent in organic chemistry. Numerous examples of the successful use of (TMS)3SiH in radical reductions, hydrosilylation and consecutive radical reactions are given. The use of (TMS)3SiH allows reactions to be carried out under mild conditions with excellent yields of products and remarkable chemo-, regio-, and stereoselectivity. The strategic role of (TMS)3SiH in polymerization is underlined with emphasis on the photo-induced radical polymerization of olefins and photo-promoted cationic polymerization of epoxides. Full article
(This article belongs to the Special Issue Organosilicon Chemistry)

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