Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

• Published in: ChemCatChem Vol. 10; no. 23; pp. 5342 - 5365
• Main Authors: Herrmann, Norman, Vogelsang, Dennis, Behr, Arno, Seidensticker, Thomas
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 07.12.2018
• Subjects: 1,3-butadiene; 1,3-dienes; Agrochemicals; Butadiene; Carbon dioxide; Catalysis; Chemical industry; Cyclopentadiene; Detergents; Dienes; Fine chemicals; Fragrances; functionalization; homogeneous catalysis; Isoprene; Low molecular weights; Naphtha; Organic chemistry; renewables; Substrates; Transition metals
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.201801362

For many years, the efficient use of resources has been a major and permanent challenge for the chemical industry. The implementation of alternative resources such as renewables and carbon dioxide has been a subject of considerable discussion, but also the more efficient use of long known bulk chemicals is of great interest. Among them, 1,3‐dienes such as 1,3‐butadiene from the C4 cut of the naphtha cracker as well as isoprene, piperylene and cyclopentadiene from the corresponding C5 section are important substrates. These dienes are presently employed in various markets, with the greatest importance being in the production of polymers and copolymers. However, homogeneous transition metal catalysis has proven to be a versatile tool to functionalize these important 1,3‐dienes to low molecular weight fine chemicals by introducing, for example, nitrogen, oxygen or silicon. Hence, an upgraded use of the corresponding products as agrochemicals, pharmaceuticals, fragrances or special detergents is close at hand. The main approaches in the topic of homogeneous functionalization reactions of the industrially relevant 1,3‐dienes will be summarized and discussed within the present article. Besides that, novel applications including renewable 1,3‐dienes, for example β‐myrcene and β‐farnesene, as well as the application of CO2 in telomerization, will be critically discussed. Going all the way! Homogeneous transition metal catalysis is a very potent tool to functionalize 1,3‐dienes to low molecular weight fine chemicals. This Review covers functionalization reactions of the fossil‐based 1,3‐butadiene, isoprene, piperylene, cyclopentadiene and bio‐mass based β‐myrcene and β‐farnesene. A differentiation between industrially established processes and those that have been tested on laboratory and miniplant scale in academia is made. The different examples are presented in a well‐structured order and critically discussed, stimulating scientists to pay more attention to these chemicals for producing versatile compounds through homogeneous catalysis.