Xantphos‐ligated palladium dithiolates: An unprecedented and convenient catalyst for the carbonylative Suzuki–Miyaura cross‐coupling reaction with high turnover number and turnover frequency

Abstract

Xantphos‐ and dithiolate‐ligated macrocyclic palladium complexes as an efficient and stable catalyst for the carbonylative Suzuki–Miyaura cross‐coupling reaction have been synthesized. The catalysts were characterized by 1 H‐nuclear magnetic resonance (NMR), CHNS (carbon, hydrogen, nitrogen, and sulfur) analysis, melting point analysis, and 31 P‐NMR spectroscopy. Several sensitive functional groups (e.g., –NO 2 , –F, –Cl, –Br, –NH 2 , and –CN) on the aromatic ring were well tolerated in the carbonylative Suzuki–Miyaura coupling reaction. The present palladium complexes produce six times higher turnover number (TON) and five times higher turnover frequency (TOF) compared with conventional homogeneous palladium precursors. Maximum TONs in the range of 10 5 to 10 6 and TOF in the range of 10 4 to 10 5 could be generated by a very low amount of catalyst loading (10 –5 mol%).