One-Pot Sequential Kumada–Tamao–Corriu Couplings of (Hetero)Aryl Polyhalides in the Presence of Grignard-Sensitive Functional Groups Using Pd-PEPPSI-IPent Cl

Narayan Sinha, Pier Alexandre Champagne, Michael J. Rodriguez, Yu Lu, Michael E. Kopach, David Mitchell, Michael G. Organ

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

We report a general and rapid chemoselective Kumada–Tamao–Corriu (KTC) cross-coupling of aryl bromides in the presence of chlorides or triflates with functionalized Grignard reagents at 0 °C in 15 min by using Pd-PEPPSI-IPent Cl (C4). Nucleophiles and electrophiles (or both) can contain Grignard-sensitive functional groups (-CN, -COOR, etc.). Control experiments together with DFT calculations suggest that transmetallation is rate limiting for the selective cross-coupling of Br in the presence of Cl/OTf with functionalized Grignard reagents. One-pot sequential KTC/KTC cross-couplings with bromo–chloro arenes have been demonstrated for the first time. We also report the one-pot sequential KTC/Negishi cross-couplings using C4 showcasing the versatility of this methodology.

Original languageEnglish (US)
Pages (from-to)6508-6512
Number of pages5
JournalChemistry - A European Journal
Volume25
Issue number26
DOIs
StatePublished - May 7 2019
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Keywords

  • Pd-PEPPSI
  • chemoselective coupling
  • cross-coupling
  • functionalized Grignard reagents
  • sequential coupling

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