Volume 19, Issue 2 pp. 182-187

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Reactions of polycyclic thioketones with a phosphonylated carbanion^†

Grzegorz Mloston,

Corresponding Author

Grzegorz Mloston

[email protected]

Section of Heteroorganic Compounds, University of Lodz, Narutowicza 68, PL-90-136 Lodz, Poland

Grzegorz Mloston, Section of Heteroorganic Compounds, University of Lodz, Narutowicza 68, PL-90-136 Lodz, Poland

Heinz Heimgartner, Institute of Organic Chemistry, University of Zurich, Winterthurerstr. 190, CH-8057 Zurich, Switzerland

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Emilia Obijalska,

Emilia Obijalska

Section of Heteroorganic Compounds, University of Lodz, Narutowicza 68, PL-90-136 Lodz, Poland

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Katarzyna Urbaniak,

Katarzyna Urbaniak

Section of Heteroorganic Compounds, University of Lodz, Narutowicza 68, PL-90-136 Lodz, Poland

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Heinz Heimgartner,

Corresponding Author

Heinz Heimgartner

[email protected]

Institute of Organic Chemistry, University of Zurich, Winterthurerstr. 190, CH-8057 Zurich, Switzerland

Grzegorz Mloston, Section of Heteroorganic Compounds, University of Lodz, Narutowicza 68, PL-90-136 Lodz, Poland

Heinz Heimgartner, Institute of Organic Chemistry, University of Zurich, Winterthurerstr. 190, CH-8057 Zurich, Switzerland

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Grzegorz Mloston,

Corresponding Author

Grzegorz Mloston

[email protected]

Section of Heteroorganic Compounds, University of Lodz, Narutowicza 68, PL-90-136 Lodz, Poland

Grzegorz Mloston, Section of Heteroorganic Compounds, University of Lodz, Narutowicza 68, PL-90-136 Lodz, Poland

Heinz Heimgartner, Institute of Organic Chemistry, University of Zurich, Winterthurerstr. 190, CH-8057 Zurich, Switzerland

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Emilia Obijalska,

Emilia Obijalska

Section of Heteroorganic Compounds, University of Lodz, Narutowicza 68, PL-90-136 Lodz, Poland

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Katarzyna Urbaniak,

Katarzyna Urbaniak

Section of Heteroorganic Compounds, University of Lodz, Narutowicza 68, PL-90-136 Lodz, Poland

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Heinz Heimgartner,

Corresponding Author

Heinz Heimgartner

[email protected]

Institute of Organic Chemistry, University of Zurich, Winterthurerstr. 190, CH-8057 Zurich, Switzerland

Grzegorz Mloston, Section of Heteroorganic Compounds, University of Lodz, Narutowicza 68, PL-90-136 Lodz, Poland

Heinz Heimgartner, Institute of Organic Chemistry, University of Zurich, Winterthurerstr. 190, CH-8057 Zurich, Switzerland

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First published: 04 March 2008

https://doi.org/10.1002/hc.20390

Citations: 8

^†

Dedicated to Prof. M. Mikolajczyk on the occasion of his 70th birthday.

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Abstract

Polycyclic, nonenolizable cycloaliphatic thioketones 1a and 1b react smoothly with the lithium salt of diethyl methylphosphonate 7 in THF solution at −40°C to afford products of the carbophilic attack exclusively. Quenching of the obtained lithium thiolates with alkyl iodides yields sulfanes of type 9 or 11, respectively, in good yields. 1-Fluoro-2,4-dinitrobenzene was shown to act as an arylating agent. In the case of the “cage” thioketone 1b, the carbanion of salt 7 approaches the CS bond from the exo-side exclusively. In contrast to the parent carbonyl compounds, thioketones 1 show no tendency to undergo the conversion analogous to the Horner–Wadsworth–Emmons reaction, which would result in the formation of an olefinic product. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:182–187, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20390

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Reactions of polycyclic thioketones with a phosphonylated carbanion^†