Synthesis of Pyrrole-2-Carboxylic Acid from Cellulose- and Chitin-Based Feedstocks Discovered by the Automated Route Search

Abstract

The shift towards sustainable feedstocks for platform chemicals requires new routes to access functional molecules that contain heteroatoms, but there are limited bio-derived feedstocks that lead to heteroatoms in platform chemicals. Combining renewable molecules of different origins could be a solution to optimize the use of atoms from renewable sources. However, the lack of retrosynthetic tools makes it challenging to examine the extensive reaction networks of various platform molecules focusing on multiple bio-based feedstocks. In this study, a protocol was developed to identify potential transformation pathways that allow for the use of feedstocks from different origins. By analyzing existing knowledge on chemical reactions in large databases, several promising synthetic routes were shortlisted, with the reaction of D-glucosamine and pyruvic acid being the most interesting to make pyrrole-2-carboxylic acid (PCA). The optimized synthetic conditions resulted in 50 % yield of PCA, with insights gained from temperature variant NMR studies. The use of substrates obtained from two different bio-feedstock bases, namely cellulose and chitin, allowed for the establishment of a PCA-based chemical space.