Modular Synthesis of Unsymmetrical 1,1’‐Disubstituted Ferrocenes by Sequential Suzuki‐Miyaura Cross‐Coupling of 1,1’‐Diborylferrocene

Unsymmetrical 1,1'-disubstituted ferrocene is a versatile scaffold for various functional molecules, including organic electronics, catalysts, and bioactive molecules. Herein, we report a facile synthesis of unsymmetrical 1,1'-disubstituted ferrocene derivatives based on the desymmetrization of 1,1'-diborylferrocene. We found that Suzuki-Miyaura cross-coupling (SMCC) reaction using 1,1'-bis(Bpin)ferrocene affords the mono-substituted product without significant loss of the second boryl group. Then, second SMCC reaction of the obtained 1-aryl-1'-(Bpin)ferrocene affords the desired unsymmetrical 1,1'-disubstituted ferrocene derivatives in reasonable yields. This method provides a versatile synthetic platform for tuning the electronic and steric properties of functional ferrocene derivatives and for the structural development of bioactive compounds.