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One‐Pot Sequential Kumada–Tamao–Corriu Couplings of (Hetero)Aryl Polyhalides in the Presence of Grignard‐Sensitive Functional Groups Using Pd‐PEPPSI‐IPent Cl
Author(s) -
Sinha Narayan,
Champagne Pier Alexandre,
Rodriguez Michael J.,
Lu Yu,
Kopach Michael E.,
Mitchell David,
Organ Michael G.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901150
Subject(s) - negishi coupling , aryl , electrophile , transmetalation , chemistry , nucleophile , reagent , combinatorial chemistry , medicinal chemistry , organic chemistry , catalysis , alkyl
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.