Transition metal-catalyzed cross-coupling reactions of alkyl sulfones as crystalline and readily available alkyl electrophiles via a radical process are highlighted.
ABSTRACT: Although the catalytic carboxylation of unactivated alkyl electrophiles has reached remarkable levels of sophistication, the intermediacy of (phenanthroline)Ni(I)-alkyl species – complexes proposed in numerous Ni-catalyzed reductive cross-coupling reactions – has been subject to speculation. Herein, we report the synthesis of such elusive (phenanthroline)Ni(I) species and their reactivity with CO2, allowing us to address a long-standing challenge related to metal-catalyzed carboxylation reactions. <div>
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ABSTRACT: Although the catalytic carboxylation of unactivated alkyl electrophiles has reached remarkable levels of sophistication, the intermediacy of (phenanthroline)Ni(I)-alkyl species – complexes proposed in numerous Ni-catalyzed reductive cross-coupling reactions – has been subject to speculation. Herein, we report the synthesis of such elusive (phenanthroline)Ni(I) species and their reactivity with CO2, allowing us to address a long-standing challenge related to metal-catalyzed carboxylation reactions. <div>
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Ni(I)-Alkyl Complexes Bearing Phenanthroline Ligands: Experimental Evidence for CO2 Insertion at Ni(I) Centers