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Freitag, Frederik; Irrgang, Torsten; Kempe, Rhett
Chemistry : a European journal, September 7, 2017, Volume: 23, Issue: 50Journal Article
Alcohols are promising sustainable starting materials because they can be obtained from abundant and indigestible biomass. The substitution of expensive noble metals in catalysis by earth abundant 3d metals, such as Mn, Fe, or Co, (nonprecious or base metals) is a related key concept with respect to sustainability. Here, we report on the first cobalt‐catalyzed alkylation of secondary alcohols with primary alcohols. Easy‐to‐synthesize and easy‐to‐activate PN5P‐pincer‐ligand‐stabilized Co complexes developed in our laboratory mediate the reaction most efficiently. The catalysis is applicable to a broad substrate scope and proceeds under relatively mild conditions. We have even demonstrated the coupling of a variety of purely aliphatic alcohols with a base or nonprecious metal catalyst. Mechanistic studies indicate that the reaction follows the borrowing hydrogen or hydrogen autotransfer concept. It is all about the alCohol: The first cobalt catalyst for the alkylation of secondary alcohols with primary alcohols is reported. The system requires mild conditions with a high substrate scope, even for aliphatic motifs, and yields of the isolated products of up to 80 %.
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