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
- 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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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.more » « less
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