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Total Synthesis and Structure Confirmation of Elatenyne: Success of Computational Methods for NMR Prediction with Highly Flexible Diastereomers

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posted on 18.07.2012, 00:00 by Bryony S. Dyson, Jonathan W. Burton, Te-ik Sohn, Byungsook Kim, Hoon Bae, Deukjoon Kim
Elatenyne is a small dibrominated natural product first isolated from Laurencia elata. The structure of elatenyne was originally assigned as a pyrano­[3,2-b]­pyran on the basis of NMR methods. Total synthesis of the originally proposed pyrano­[3,2-b]­pyran structure of elatenyne led to the gross structure of the natural product being reassigned as a 2,2′-bifuranyl. The full stereostructure of this highly flexible small molecule was subsequently predicted by Boltzmann-weighted DFT calculations of 13C NMR chemical shifts for all 32 potential diastereomers, with the predicted structure being in accord with the proposed biogenesis outlined below. Herein we report two complementary total syntheses of elatenyne, which confirm the computer-predicted stereostructure. Additionally, the total syntheses of (E)-elatenyne and a related 2,2′-bifuranyl, laurendecumenyne B, are reported. This work has not only allowed the full structure determination of all of these natural products but also provides excellent supporting evidence for their proposed biogenesis. The total synthesis of elatenyne demonstrates that DFT calculations of 13C NMR chemical shifts coupled with biosynthetic postulates, comprise a very useful method for distinguishing among large numbers of highly flexible, closely related molecules.