Ring-Opening Lithiation–Borylation of 2-Trifluoromethyl Oxirane: A Route to Versatile Tertiary Trifluoromethyl Boronic Esters

Meganathan Nandakumar, Belén Rubial, Adam Noble, Eddie L. Myers*, Varinder K. Aggarwal

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

4 Citations (Scopus)
28 Downloads (Pure)

Abstract

Stereogenic trifluoromethyl-substituted carbon centers are highly sought-after moieties in pharmaceutical and agrochemical discovery. Here, we show that lithiation–borylation reactions of 2-trifluoromethyl oxirane give densely functionalized and highly versatile trifluoromethyl-substituted α-tertiary boronic esters. The intermediate boronate complexes undergo the desired 1,2-rearrangement of the carbon-based group with complete retentive stereospecificity, a process that was only observed in non-polar solvents in the presence of TESOTf. Although the trifluoromethyl group adversely affects subsequent transformations of the α-boryl group, Zweifel olefinations provide trifluoromethyl-bearing quaternary stereocenters substituted with alkenes, alkynes and ketones.

Original languageEnglish
Pages (from-to)1187-1191
Number of pages5
JournalAngewandte Chemie - International Edition
Volume59
Issue number3
Early online date11 Nov 2019
DOIs
Publication statusPublished - 13 Jan 2020

Keywords

  • fluorine
  • lithiation–borylation
  • quaternary center
  • stereospecific synthesis
  • trifluoromethyl

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