Total Synthesis and Structure Confirmation of Elatenyne: Success of Computational Methods for NMR Prediction with Highly Flexible Diastereomers.
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| Title: | Total Synthesis and Structure Confirmation of Elatenyne: Success of Computational Methods for NMR Prediction with Highly Flexible Diastereomers. |
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| Authors: | Dyson, Bryony S.1, Burton, Jonathan W.1 jonathan.burton@chem.ox.ac.uk, Te-ik Sohn2, Byungsook Kim2, Hoon Bae2, Deukjoon Kim2 deukjoon@snu.ac.kr |
| Source: | Journal of the American Chemical Society. 7/18/2012, Vol. 134 Issue 28, p11781-11790. 10p. |
| Subjects: | Natural products, Biosynthesis, Laurencia, Algae products, Diastereoisomers, Molecular structure |
| Abstract: | 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. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 78130150 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Total Synthesis and Structure Confirmation of Elatenyne: Success of Computational Methods for NMR Prediction with Highly Flexible Diastereomers. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Dyson%2C+Bryony+S%2E%22">Dyson, Bryony S.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Burton%2C+Jonathan+W%2E%22">Burton, Jonathan W.</searchLink><relatesTo>1</relatesTo><i> jonathan.burton@chem.ox.ac.uk</i><br /><searchLink fieldCode="AR" term="%22Te-ik+Sohn%22">Te-ik Sohn</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Byungsook+Kim%22">Byungsook Kim</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Hoon+Bae%22">Hoon Bae</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Deukjoon+Kim%22">Deukjoon Kim</searchLink><relatesTo>2</relatesTo><i> deukjoon@snu.ac.kr</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Chemical+Society%22">Journal of the American Chemical Society</searchLink>. 7/18/2012, Vol. 134 Issue 28, p11781-11790. 10p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Natural+products%22">Natural products</searchLink><br /><searchLink fieldCode="DE" term="%22Biosynthesis%22">Biosynthesis</searchLink><br /><searchLink fieldCode="DE" term="%22Laurencia%22">Laurencia</searchLink><br /><searchLink fieldCode="DE" term="%22Algae+products%22">Algae products</searchLink><br /><searchLink fieldCode="DE" term="%22Diastereoisomers%22">Diastereoisomers</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: 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. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/ja304554e Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 10 StartPage: 11781 Subjects: – SubjectFull: Natural products Type: general – SubjectFull: Biosynthesis Type: general – SubjectFull: Laurencia Type: general – SubjectFull: Algae products Type: general – SubjectFull: Diastereoisomers Type: general – SubjectFull: Molecular structure Type: general Titles: – TitleFull: Total Synthesis and Structure Confirmation of Elatenyne: Success of Computational Methods for NMR Prediction with Highly Flexible Diastereomers. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Dyson, Bryony S. – PersonEntity: Name: NameFull: Burton, Jonathan W. – PersonEntity: Name: NameFull: Te-ik Sohn – PersonEntity: Name: NameFull: Byungsook Kim – PersonEntity: Name: NameFull: Hoon Bae – PersonEntity: Name: NameFull: Deukjoon Kim IsPartOfRelationships: – BibEntity: Dates: – D: 18 M: 07 Text: 7/18/2012 Type: published Y: 2012 Identifiers: – Type: issn-print Value: 00027863 Numbering: – Type: volume Value: 134 – Type: issue Value: 28 Titles: – TitleFull: Journal of the American Chemical Society Type: main |
| ResultId | 1 |
