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One-Pot Sequential Kumada-Tamao-Corriu Couplings of (Hetero)Aryl Polyhalides in the Presence of Grignard-Sensitive
Narayan Sinha1,2, Pier Alexandre Champagne2, Michael J Rodriguez3
1Department of Chemistry, York University, 4700 Keele Street, Toronto, Ontario, M3J 1P3, Canada.
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-IPentCl (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.
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