Biobased Ligands Enable Catalysis with Base Metals

First‐row transition metal catalysis has already reshaped organic synthesis, offering more abundant and cost‐effective alternatives to precious metals. However, the design of sustainable alternatives for the ligands that dictate metal reactivity remains an unresolved issue. In this work, we demonstrate that phosphines and phosphinites assembled from renewable building blocks can enable catalytic transformations mediated by base metals such as Cu, Ni, and Fe. Hydroboration of olefins, borylation of alkyl halides, hydrogenation of ketones, and dimerization of terminal alkynes are now achievable using homogeneous catalysts based on 3d metals and biobased ligands. The mild reaction conditions established in this study facilitate, among other applications, the late‐stage functionalization of pharmaceuticals, such as bexarotene, estrone, and nabumetone.