Stoichiometric Studies on the Carbonylative Trifluoromethylation of Aryl Pd(II) Complexes using TMSCF3 as the Trifluoromethyl Source

Katrine Domino, Martin B. Johansen, Kim Daasbjerg, Troels Skrydstrup*

*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaperJournal articleResearchpeer-review

Abstract

We have performed a series of stoichiometric studies in order to identify viable steps for a hypothetical catalytic cycle for the palladium-mediated carbonylative coupling of an aryl bromide with TMSCF3. Our work revealed that benzoyl Pd(II) complexes bearing Xantphos or tBu(3)P as the phosphine ligands, which are generated from the corresponding Pd-II(Ph)Br complexes exposed to stoichiometric (CO)-C-13 from (13)COgen, were unable to undergo transmetalation and reductive elimination to trifluor-oacetophenone. Instead, in the presence of base and additional CO, these organometallic complexes readily underwent reductive elimination to the acid fluoride. Attempts to determine whether the acid fluoride could represent an intermediate for acetophenone production were unrewarding. Only in the presence of a boronic ester did we observe some formation of the desired product, although the efficiency of transformation was still low. Finally, we investigated the reactivity of four phosphine-ligated Pd-II(Ph)CF3 complexes (Xantphos, DtBPF, tBu(3)P, and triphenylphosphine) with carbon monoxide. With the exception of the tBu(3)P-ligated complex, all other metal complexes led to the facile formation of trifluoroacetophenone. We also determined in the case of triphenylphosphine that CO insertion occurred into the Pd-Ar bond, as trapping of this complex with n-hexylamine led to the formation of n-hexylbenzamide.

Original languageEnglish
JournalOrganometallics
Volume39
Issue5
Pages (from-to)688-697
Number of pages10
ISSN0276-7333
DOIs
Publication statusPublished - 9 Mar 2020

Keywords

  • ACID FLUORIDE
  • BROMIDES
  • CARBON-CARBON
  • CATALYZED TRIFLUOROMETHYLATION
  • CHLORIDES
  • EX-SITU GENERATION
  • FORMING REDUCTIVE ELIMINATION
  • KETONES
  • PD
  • PHARMACEUTICALS

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