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Huang YC, Nguyen A, Gräßle S, et al. Addition of dithi(ol)anylium tetrafluoroborates to α,β-unsaturated ketones. Beilstein J Org Chem. 2018;14:515-522doi: 10.3762/bjoc.14.37.
Huang, Y. C., Nguyen, A., Gräßle, S., Vanderheiden, S., Jung, N., & Bräse, S. (2018). Addition of dithi(ol)anylium tetrafluoroborates to α,β-unsaturated ketones. Beilstein journal of organic chemistry, 14515-522. https://doi.org/10.3762/bjoc.14.37
Huang, Yu-Chieh, et al. "Addition of dithi(ol)anylium tetrafluoroborates to α,β-unsaturated ketones." Beilstein journal of organic chemistry vol. 14 (2018): 515-522. doi: https://doi.org/10.3762/bjoc.14.37
Huang YC, Nguyen A, Gräßle S, Vanderheiden S, Jung N, Bräse S. Addition of dithi(ol)anylium tetrafluoroborates to α,β-unsaturated ketones. Beilstein J Org Chem. 2018 Feb 26;14:515-522. doi: 10.3762/bjoc.14.37. eCollection 2018. PMID: 29623112; PMCID: PMC5852463.
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Beilstein J Org Chem. 2018 Feb 26;14:515-522. doi: 10.3762/bjoc.14.37. eCollection 2018.

Addition of dithi(ol)anylium tetrafluoroborates to α,β-unsaturated ketones.

Beilstein journal of organic chemistry

Yu-Chieh Huang, An Nguyen, Simone Gräßle, Sylvia Vanderheiden, Nicole Jung, Stefan Bräse

Affiliations

  1. Institute of Toxicology and Genetics, Karlsruhe Institute of Technology, Campus North, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
  2. Institute of Organic Chemistry, Karlsruhe Institute of Technology, Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany.

PMID: 29623112 PMCID: PMC5852463 DOI: 10.3762/bjoc.14.37

Abstract

In the presented study, dithi(ol)anylium tetrafluoroborates are added to α,β-unsaturated ketones in a Michael-type reaction yielding diverse substituted ketene diothi(ol)anes. The reactions proceed at room temperature in 1 or 13 h without the need of further additives. The presented procedure is in particular useful for dithi(ol)anylium tetrafluoroborates without electron-withdrawing groups in α-position. This is advantageous with respect to previous approaches, which were limited to the use of ketene dithioacetals substituted with electron-withdrawing groups. Aiming for the systematic investigation of possible steric and electronic influences on the outcome of the reaction, various combinations of electrophiles and nucleophiles were used and the results of the reactions were compared based on the type of the used dithioacetal. The scope of the presented procedure is shown with four additional transformations including the use of additional electrophiles and nucleophiles, the use of a chiral auxiliary and subsequent reduction of selected products. Additionally, we extended the reaction to the synthesis of diene dithiolanes by addition of an ynone to α-alkyl or aryl-substitued dithiolanylium TFBs.

Keywords: addition to α,β-unsaturated carbonyls; dithiane chemistry; dithianylium tetrafluoroborate (TFB); ketene dithiane

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