1,1,3,3-Tetrakis(alkylthio)-1,3-dilithio-2-silapropanes: Useful reagents for the synthesis of polysilacycloalkanes via dianionic ring formation

Masaki Shimizu, Masayuki Iwakubo, Yasushi Nishihara, Katsunari Oda, Tamejiro Hiyama

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Treatment of 1,1,3,3-tetrakis(alkylthio)-2-silapropanes with t-BuLi in THF at -40°C generated 1,1,3,3-tetrakis(alkylthio)-1,3-dilithio-2-silapropanes which reacted with various bifunctional chlorosilanes to give the corresponding 4- to 7-membered polysilacycloalkanes in moderate to good yields. Furthermore, double alkylation of the dilithiated silanes with bis(halomethyl)diorganosilanes or dihaloalkanes was found to proceed smoothly giving rise to 1,4-disilacyclohexanes or silacycloalkanes in good yields, respectively, in THF and an aprotic polar co-solvent such as hexamethylphosphoric triamide (HMPA) or 1,1,3,3-tetramethylurea (TMU). The sulfenyl groups in the cyclized products were smoothly removed by radical reduction with tributyltin hydride.

Original languageEnglish
Pages (from-to)29-48
Number of pages20
JournalArkivoc
Volume2007
Issue number10
Publication statusPublished - 2007

Fingerprint

Hempa
Silanes
Alkylation
tributyltin
1,1,3,3-tetramethylurea

Keywords

  • Dianion
  • Lithium
  • Polysilacycloalkane
  • Silicon

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

1,1,3,3-Tetrakis(alkylthio)-1,3-dilithio-2-silapropanes : Useful reagents for the synthesis of polysilacycloalkanes via dianionic ring formation. / Shimizu, Masaki; Iwakubo, Masayuki; Nishihara, Yasushi; Oda, Katsunari; Hiyama, Tamejiro.

In: Arkivoc, Vol. 2007, No. 10, 2007, p. 29-48.

Research output: Contribution to journalArticle

Shimizu, Masaki ; Iwakubo, Masayuki ; Nishihara, Yasushi ; Oda, Katsunari ; Hiyama, Tamejiro. / 1,1,3,3-Tetrakis(alkylthio)-1,3-dilithio-2-silapropanes : Useful reagents for the synthesis of polysilacycloalkanes via dianionic ring formation. In: Arkivoc. 2007 ; Vol. 2007, No. 10. pp. 29-48.
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abstract = "Treatment of 1,1,3,3-tetrakis(alkylthio)-2-silapropanes with t-BuLi in THF at -40°C generated 1,1,3,3-tetrakis(alkylthio)-1,3-dilithio-2-silapropanes which reacted with various bifunctional chlorosilanes to give the corresponding 4- to 7-membered polysilacycloalkanes in moderate to good yields. Furthermore, double alkylation of the dilithiated silanes with bis(halomethyl)diorganosilanes or dihaloalkanes was found to proceed smoothly giving rise to 1,4-disilacyclohexanes or silacycloalkanes in good yields, respectively, in THF and an aprotic polar co-solvent such as hexamethylphosphoric triamide (HMPA) or 1,1,3,3-tetramethylurea (TMU). The sulfenyl groups in the cyclized products were smoothly removed by radical reduction with tributyltin hydride.",
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AU - Iwakubo, Masayuki

AU - Nishihara, Yasushi

AU - Oda, Katsunari

AU - Hiyama, Tamejiro

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N2 - Treatment of 1,1,3,3-tetrakis(alkylthio)-2-silapropanes with t-BuLi in THF at -40°C generated 1,1,3,3-tetrakis(alkylthio)-1,3-dilithio-2-silapropanes which reacted with various bifunctional chlorosilanes to give the corresponding 4- to 7-membered polysilacycloalkanes in moderate to good yields. Furthermore, double alkylation of the dilithiated silanes with bis(halomethyl)diorganosilanes or dihaloalkanes was found to proceed smoothly giving rise to 1,4-disilacyclohexanes or silacycloalkanes in good yields, respectively, in THF and an aprotic polar co-solvent such as hexamethylphosphoric triamide (HMPA) or 1,1,3,3-tetramethylurea (TMU). The sulfenyl groups in the cyclized products were smoothly removed by radical reduction with tributyltin hydride.

AB - Treatment of 1,1,3,3-tetrakis(alkylthio)-2-silapropanes with t-BuLi in THF at -40°C generated 1,1,3,3-tetrakis(alkylthio)-1,3-dilithio-2-silapropanes which reacted with various bifunctional chlorosilanes to give the corresponding 4- to 7-membered polysilacycloalkanes in moderate to good yields. Furthermore, double alkylation of the dilithiated silanes with bis(halomethyl)diorganosilanes or dihaloalkanes was found to proceed smoothly giving rise to 1,4-disilacyclohexanes or silacycloalkanes in good yields, respectively, in THF and an aprotic polar co-solvent such as hexamethylphosphoric triamide (HMPA) or 1,1,3,3-tetramethylurea (TMU). The sulfenyl groups in the cyclized products were smoothly removed by radical reduction with tributyltin hydride.

KW - Dianion

KW - Lithium

KW - Polysilacycloalkane

KW - Silicon

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