Sila-Peterson Reaction of Cyclic Silanides

Andreas W. Kyri; Lukas Schuh; Andreas Knoechl; Michael Schalli; Ana Torvisco; Roland C. Fischer; Michael Haas; Harald Stueger

doi:10.1021/acs.organomet.0c00106

Sila-Peterson Reaction of Cyclic Silanides

Andreas W. Kyri, Lukas Schuh, Andreas Knoechl, Michael Schalli, Ana Torvisco, Roland C. Fischer, Michael Haas, Harald Stueger^*

^*Corresponding author for this work

Institute of Inorganic Chemistry (6330)

Research output: Contribution to journal › Article › peer-review

Abstract

Sila-Peterson type reactions of the 1,4,4-tris(trimethylsilyl)-1-metallooctamethylcyclohexasilanes (Me3Si)2Si6Me8(SiMe3)M (2a, M = Li; 2b, M = K) with various ketones were investigated. The obtained products strongly depend on the nature of the ketone component. With 2-adamantanone 2a,b afforded the moderately stable silene 3. 3 is the first example of an Apeloig-Ishikawa-Oehme-type silene with the tricoordinate silicon atom incorporated into a cyclopolysilane framework and could be characterized by NMR and UV spectroscopy as well as by trapping reactions with water, methanol, and MeLi. The reaction of 2b with aromatic ketones also follows a sila-Peterson type mechanism with formation of carbanionic species. With 1,2-diphenylcyclopropenone 2b reacted by conjugate 1,4-addition to give a spirocyclic carbanion. In most cases the underlying reaction mechanism could be elucidated by the isolation and characterization of unstable intermediates and final products after proper derivatization.

Original language	English
Pages (from-to)	1832-1841
Number of pages	10
Journal	Organometallics
Volume	39
Issue number	10
DOIs	https://doi.org/10.1021/acs.organomet.0c00106
Publication status	Published - 26 May 2020

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Sila-Peterson Reaction of Cyclic Silanides",

abstract = "Sila-Peterson type reactions of the 1,4,4-tris(trimethylsilyl)-1-metallooctamethylcyclohexasilanes (Me3Si)2Si6Me8(SiMe3)M (2a, M = Li; 2b, M = K) with various ketones were investigated. The obtained products strongly depend on the nature of the ketone component. With 2-adamantanone 2a,b afforded the moderately stable silene 3. 3 is the first example of an Apeloig-Ishikawa-Oehme-type silene with the tricoordinate silicon atom incorporated into a cyclopolysilane framework and could be characterized by NMR and UV spectroscopy as well as by trapping reactions with water, methanol, and MeLi. The reaction of 2b with aromatic ketones also follows a sila-Peterson type mechanism with formation of carbanionic species. With 1,2-diphenylcyclopropenone 2b reacted by conjugate 1,4-addition to give a spirocyclic carbanion. In most cases the underlying reaction mechanism could be elucidated by the isolation and characterization of unstable intermediates and final products after proper derivatization. ",

author = "Kyri, {Andreas W.} and Lukas Schuh and Andreas Knoechl and Michael Schalli and Ana Torvisco and Fischer, {Roland C.} and Michael Haas and Harald Stueger",

year = "2020",

month = may,

day = "26",

doi = "10.1021/acs.organomet.0c00106",

language = "English",

volume = "39",

pages = "1832--1841",

journal = "Organometallics",

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T1 - Sila-Peterson Reaction of Cyclic Silanides

AU - Kyri, Andreas W.

AU - Schuh, Lukas

AU - Knoechl, Andreas

AU - Schalli, Michael

AU - Torvisco, Ana

AU - Fischer, Roland C.

AU - Haas, Michael

AU - Stueger, Harald

PY - 2020/5/26

Y1 - 2020/5/26

N2 - Sila-Peterson type reactions of the 1,4,4-tris(trimethylsilyl)-1-metallooctamethylcyclohexasilanes (Me3Si)2Si6Me8(SiMe3)M (2a, M = Li; 2b, M = K) with various ketones were investigated. The obtained products strongly depend on the nature of the ketone component. With 2-adamantanone 2a,b afforded the moderately stable silene 3. 3 is the first example of an Apeloig-Ishikawa-Oehme-type silene with the tricoordinate silicon atom incorporated into a cyclopolysilane framework and could be characterized by NMR and UV spectroscopy as well as by trapping reactions with water, methanol, and MeLi. The reaction of 2b with aromatic ketones also follows a sila-Peterson type mechanism with formation of carbanionic species. With 1,2-diphenylcyclopropenone 2b reacted by conjugate 1,4-addition to give a spirocyclic carbanion. In most cases the underlying reaction mechanism could be elucidated by the isolation and characterization of unstable intermediates and final products after proper derivatization.

AB - Sila-Peterson type reactions of the 1,4,4-tris(trimethylsilyl)-1-metallooctamethylcyclohexasilanes (Me3Si)2Si6Me8(SiMe3)M (2a, M = Li; 2b, M = K) with various ketones were investigated. The obtained products strongly depend on the nature of the ketone component. With 2-adamantanone 2a,b afforded the moderately stable silene 3. 3 is the first example of an Apeloig-Ishikawa-Oehme-type silene with the tricoordinate silicon atom incorporated into a cyclopolysilane framework and could be characterized by NMR and UV spectroscopy as well as by trapping reactions with water, methanol, and MeLi. The reaction of 2b with aromatic ketones also follows a sila-Peterson type mechanism with formation of carbanionic species. With 1,2-diphenylcyclopropenone 2b reacted by conjugate 1,4-addition to give a spirocyclic carbanion. In most cases the underlying reaction mechanism could be elucidated by the isolation and characterization of unstable intermediates and final products after proper derivatization.

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DO - 10.1021/acs.organomet.0c00106

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Sila-Peterson Reaction of Cyclic Silanides

Abstract

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