The first cobalt‐catalyzed cross‐coupling of aryl tosylates with alkyl and aryl Grignard reagents is reported. The catalytic system uses CoF3and NHCs (NHC=N‐heterocyclic carbene) as ancillary ligands. The reaction proceeds via highly selective C−O bond functionalization, leading to the corresponding products in up to 98 % yield. The employment of alkyl Grignard reagents allows to achieve a rare C(sp2)−C(sp3) cross‐coupling of C−O electrophiles, circumventing isomerization and β‐hydride elimination problems. The use of aryl Grignards leads to the formation of biaryls. The C−O cross‐coupling sets the stage for a sequential cross‐coupling by exploiting the orthogonal selectivity of the catalytic system.
Chemoselective Activation of sp 3 vs sp 2 C–H Bonds with Pd(II)
- NSF-PAR ID:
- 10000038
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- Volume:
- 137
- Issue:
- 1
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- 18 to 21
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract -
A unique C(sp 3 )–H/C(sp 3 )–H dehydrocoupling of N -benzylimines with saturated heterocycles is described. Using super electron donor (SED) 2-azaallyl anions and aryl iodides as electron acceptors, single-electron-transfer (SET) generates an aryl radical. Hydrogen atom transfer (HAT) from saturated heterocycles or toluenes to the aryl radical generates alkyl radicals or benzylic radicals, respectively. The newly formed alkyl radicals and benzylic radicals couple with the 2-azaallyl radicals with formation of new C–C bonds. Experimental evidence supports the key hydrogen-abstraction by the aryl radical, which determines the chemoselectivity of the radical–radical coupling reaction. It is noteworthy that this procedure avoids the use of traditional strong oxidants and transition metals.more » « less
