The manganese-catalyzed dehydrogenative coupling between methanol and amines for the synthesis of ureas and polyureas is described. Importantly, catalytic efficiency can be improved by the newly synthesized MACHO ligands. Furthermore, this highly atom-economical protocol demonstrates a broad substrate scope with good functional group tolerance, producing H2 as the sole byproduct. Mechanistic studies disclose that formamide is formed through manganese-catalyzed formylation of amine with methanol. Subsequent dehydrogenation affords a transient isocyanate, which is attacked by another equivalent of amine to provide the final product.
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