Kashyap, R and Yerra, NV and Oja, J and Bala, S and Potuganti, GR and Thota, JR and Alla, M and Pal, D and Addlagatta, A (2021) Exo-selective intermolecular Diels�Alder reaction by PyrI4 and AbnU on non-natural substrates. In: Communications Chemistry, 4 (1).
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Abstract
The 100-year-old Diels�Alder reaction (DAr) is an atom economic and elegant organic chemistry transformation combining a 1,3-diene and a dienophile in a 4+2 cycloaddition leading to a set of products with several stereo centres and multiple stereoisomers. Stereoselective 4+2 cycloaddition is a challenge. Here, we describe two natural enzymes, PyrI4 and AbnU performing stereospecific intermolecular DAr on non-natural substrates. AbnU catalyses a single exo-stereoisomer by 32-fold higher than the background. PyrI4 catalyses the same stereoisomer (15-fold higher) as a major component (>50%). Structural, biochemical and fluorescence studies indicate that the dienophile enters first into the β-barrel of the enzymes followed by the 1,3-diene, yielding a stereospecific product. However, if some critical interactions are disrupted to increase the catalytic efficiency, stereoselectivity is compromised. Since it is established that natural enzymes can carry out intermolecular DAr on non-natural substrates, several hundreds of Diels-Alderases available in nature could be explored. © 2021, The Author(s).
| Item Type: | Journal Article |
|---|---|
| Publication: | Communications Chemistry |
| Publisher: | Nature Research |
| Additional Information: | The copyright for this article belongs to Nature Research |
| Department/Centre: | Division of Interdisciplinary Sciences > Computational and Data Sciences |
| Date Deposited: | 22 Sep 2021 10:13 |
| Last Modified: | 22 Sep 2021 10:13 |
| URI: | http://eprints.iisc.ac.in/id/eprint/69724 |
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