Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes
Abstract
Homogeneous nickel catalysis is used for the synthesis of pharmaceuticals, natural products, and polymers. These reactions generally proceed via nickel intermediates in the Ni0, NiI, NiII, and/or NiIII oxidation states. In contrast, NiIV intermediates are rarely accessible. We report herein the design, synthesis, and characterization of a series of organometallic NiIV complexes, accessed by the reaction of NiII precursors with the widely used oxidant S-(trifluoromethyl)dibenzothiophenium triflate. These NiIV complexes undergo highly selective carbon(sp3)-oxygen, carbon(sp3)-nitrogen, and carbon(sp3)-sulfur coupling reactions with exogenous nucleophiles. The observed reactivity has the potential for direct applications in the development of nickel-catalyzed carbon-heteroatom coupling reactions.
- Publication:
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Science
- Pub Date:
- March 2015
- DOI:
- 10.1126/science.aaa4526
- Bibcode:
- 2015Sci...347.1218C
- Keywords:
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- CHEMISTRY