Process Economics and Atom Economy for Industrial Cross Coupling Applications via LnPd(0)-Based Catalysts

Up to and beyond the 2010 Nobel Prize in Chemistry, Pd-based cross coupling has seen a boom in industrial applications and scientific research. These efforts have yielded a wealth of information on Pd-based catalyst technology that can be separated into two broad categories: pre-catalysts and in situ generated catalysts. Proper selection of the catalyst system, i.e., in situ vs pre-catalyst is although process dependent, herein we provide an in-depth look into the often overlooked benefits of the pre-catalyst technology for maximizing the process economics. Although ligands play a crucial role in catalysis, it is not "all about ligands" alone. To improve the efficiency of the process one may need to precisely generate the active catalytic species for that particular reaction. In this chapter, we highlighted this concept by providing industrial case studies where switching from in situ generated to pre-catalyst technology yielded significant process economic benefits. We also provided process chemists with a methodology to properly evaluate catalyst technology and make recommendations on potential benefits by weighing the pros and cons of using in situ vs preformed.