Scalable Synthesis of Norbornadienes via in situ Cracking of Dicyclopentadiene using Continuous Flow Chemistry

The Diels-Alder reaction with cyclopentadiene typically involves tedious cracking procedures from the dimer. In this contribution from the Prof. Moth-Poulsen group, it is shown how MOST photoswitches can be made on a 100 g scale in a single step combining cyclopentadiene cracking with Diels-Alder reaction using a reaction in flow.

https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ej

The norbornadiene (NBD)-quadricyclane (QC) photoswitch has recently attracted attention due to its use in molecular solar thermal energy systems (MOST). Normally for device testing, several grams are needed. One way of synthesizing NBDs efficiently is through the Diels-Alder reaction between alkynes and cyclopentadiene. However, scaling up the reaction can be troublesome in a research lab environment. Also, dicyclopentadiene needs cracking before utilization as a time-consuming step. Here, we developed a method where we both scale up the synthesis in a single reaction step that involves both in situ cracking of dicyclopentadiene and direct reaction of cyclopentadiene with acetylene derivatives using a tubular coiled stainless steel flow reactor. As a proof-of-concept, we synthesized 6 different NBD compounds, and scaled the synthesis to produce 87 g of a novel NBD in 9 h. The NBD is further characterized, showing promising properties for MOST applications. Our new method shows that flow chemistry is an attractive technique for the fast and efficient synthesis of large quantities of NBDs, needed to develop future real-life devices and applications.