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Ramb DC, Kost L, Haufe G. [3,3]-sigmatropic rearrangements of fluorinated allyl (Thio)cyanates - a tool for the synthesis of fluorinated (Thio)ureas. Chimia (Aarau). 2014;68(6):436-41doi: 10.2533/chimia.2014.436.
Ramb, D. C., Kost, L., & Haufe, G. (2014). [3,3]-sigmatropic rearrangements of fluorinated allyl (Thio)cyanates - a tool for the synthesis of fluorinated (Thio)ureas. Chimia, 68(6), 436-41. https://doi.org/10.2533/chimia.2014.436
Ramb, Daniel C, et al. "[3,3]-sigmatropic rearrangements of fluorinated allyl (Thio)cyanates - a tool for the synthesis of fluorinated (Thio)ureas." Chimia vol. 68,6 (2014): 436-41. doi: https://doi.org/10.2533/chimia.2014.436
Ramb DC, Kost L, Haufe G. [3,3]-sigmatropic rearrangements of fluorinated allyl (Thio)cyanates - a tool for the synthesis of fluorinated (Thio)ureas. Chimia (Aarau). 2014;68(6):436-41. doi: 10.2533/chimia.2014.436. PMID: 25198755.
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Chimia (Aarau). 2014;68(6):436-41. doi: 10.2533/chimia.2014.436.

[3,3]-sigmatropic rearrangements of fluorinated allyl (Thio)cyanates - a tool for the synthesis of fluorinated (Thio)ureas.

Chimia

Daniel C Ramb, Lisa Kost, Günter Haufe

Affiliations

  1. Organisch-Chemisches Institut Münster Westfälische Wilhelms-Universität Münster Corrensstraße 40, 48149 Münster, Germany.
  2. Organisch-Chemisches Institut Münster Westfälische Wilhelms-Universität Münster Corrensstraße 40, 48149 Münster, Germany. [email protected].

PMID: 25198755 DOI: 10.2533/chimia.2014.436

Abstract

The first (thio)cyanate to iso(thio)cyanate rearrangements based on 2-fluoroallylic alcohols are presented. Long-chain 2-fluoroallylic alcohols were converted to corresponding N-unsubstituted carbamates by treatment with trichloroacetyl isocyanate. Dehydration using trifluoroacetic anhydride in the presence of triethylamine formed intermediate allylic cyanates, which immediately underwent sigmatropic rearrangement to fluorinated allyl isocyanates. Without isolation the latter delivered fluorinated ureas by addition of amines. The thiocyanate to isothiocyanate rearrangements started from the same fluorinated allylic alcohols, which were first converted to mesylates. Heating in THF with potassium thiocyanate led to fluorinated allyl isothiocyanates, via [3,3]-sigmatropic rearrangement of intermediate allyl thiocyanates. The formed products were further reacted with amines to fluorinated thioureas.

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