Journal
RSC ADVANCES
Volume 13, Issue 40, Pages 27828-27838Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d3ra04406h
Keywords
-
Categories
Ask authors/readers for more resources
This study investigates the role of the absolute configuration of the C-6 carbon of the substrate polyene in the stereocontrol of the intramolecular Diels-Alder reaction (IMDA). The results show that Fsa2 exhibits consistent stereoselectivity, while Phm7 shows different stereoselectivity depending on the configuration of the 6-methyl group. The study also discovers a unique relationship between the stereochemistry of decalins and their antibacterial activity.
The intramolecular Diels-Alder reaction (IMDA) is a powerful method for regioselective and stereoselective construction of functionalised decalin skeletons, and the recent discovery of enzymes that catalyse IMDA cycloaddition in biosynthesis has generated considerable interest. This study focused on the role of the absolute configuration of the C-6 carbon of the substrate polyene in the stereocontrol of the IMDA reaction catalysed by Fsa2 and Phm7, which construct different enantiomeric decalin skeletons. Their enantiomeric precursor polyenes were synthesised and subjected to enzymatic or thermal IMDA reactions to isolate various diastereomeric decalines and determine their absolute configuration. Furthermore, density functional theory calculations were performed to elucidate the stereocontrol mechanism underlying the formation of decalin. The results showed that Fsa2 exhibits the same equisetin-type stereoselectivity for enantiomeric substrates regardless of the 6-methyl group configuration of the substrate, while Phm7 shows two types of stereoselectivity depending on the configuration of the 6-methyl group. We also found a unique stereochemistry-activity relationship in antibacterial activity for decalin diastereomers, including new derivatives. This study provides new insights into the stereoselectivity of DAase, which is important in the synthesis of natural product skeletons. This study elucidates the role of the absolute configuration at the C-6 carbon of the substrate polyene in the stereocontrol of the IMDA reaction catalyzed by Fsa2 and Phm7, which construct different enantiomeric decalin skeletons.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available