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Title: Redox Inversion: A Radical Analogue of Umpolung Reactivity for Base- and Metal-Free Catalytic C(sp 3 )–C(sp 3 ) Coupling
Award ID(s):
1954751
PAR ID:
10482936
Author(s) / Creator(s):
; ;
Publisher / Repository:
ACS
Date Published:
Journal Name:
The Journal of Organic Chemistry
Volume:
88
Issue:
6
ISSN:
0022-3263
Page Range / eLocation ID:
3935 to 3940
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. The iron-catalyzed C(sp 2 )–C(sp 3 ) cross-coupling provides a highly economical route to exceedingly valuable alkylated arenes that are widespread in medicinal chemistry and materials science. Herein, we report an operationally-simple protocol for the selective C(sp 2 )–C(sp 3 ) iron-catalyzed cross-coupling of aryl chlorides with Grignard reagents at low catalyst loading. A broad range of electronically-varied aryl and heteroaryl chlorides underwent the cross-coupling using challenging alkyl organometallics possessing β-hydrogens with high efficiency up to 2000 TON. A notable feature of the protocol is the use of environmentally-friendly cyclic urea ligands. A series of guidelines to predict cross-coupling reactivity of aryl electrophiles is provided. 
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