Biscembranoids formed from an α,β-unsaturated γ-lactone ring as a dienophile

Structure revision and establishment of their absolute configurations using theoretical calculations of electronic circular dichroism spectra

Rui Jia, T. Kurtán, Attila Mándi, Xiao Hong Yan, Wen Zhang, Yue Wei Guo

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24 Citations (Scopus)

Abstract

Four new biscembranoids, bislatumlides C-F (1-4), were isolated from the Hainan soft coral Sarcophyton latum. Their structures were elucidated by detailed analysis of spectroscopic data and by comparison with reported data of related derivatives, leading to the structure revision of co-occurring bislatumlides A (5) and B (6) at the C-21 configuration. The absolute configurations of bislatumlides C and E (1 and 3) were determined by TDDFT calculations of their solution ECD spectra, allowing the configurational assignment of the related bislatumlides D and F (2 and 4) and A and B (5 and 6) as well. Bislatumlides A-F (1-6) represent the only biscembranoids formed by the undescribed coupling pattern of Diels-Alder cycloaddition between the Δ1(2) double bond involving an α,β-unsaturated γ-lactone ring as a dienophile group and a trisubstituted conjugated Δ21(34)35(36)-butadiene moiety. An endo-cycloaddition gave 1, 2, 5, and 6, whereas an exo-cycloaddition produced 3 and 4. This is the first report of exo-addition dicembranoids from marine sources and from nature. Bislatumlides C and E (1, 3) could be used as ECD reference compounds in the determination of absolute configuration for related derivatives.

Original languageEnglish
Pages (from-to)3113-3119
Number of pages7
JournalJournal of Organic Chemistry
Volume78
Issue number7
DOIs
Publication statusPublished - Apr 5 2013

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Cycloaddition
Lactones
Derivatives

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Biscembranoids formed from an α,β-unsaturated γ-lactone ring as a dienophile: Structure revision and establishment of their absolute configurations using theoretical calculations of electronic circular dichroism spectra",
abstract = "Four new biscembranoids, bislatumlides C-F (1-4), were isolated from the Hainan soft coral Sarcophyton latum. Their structures were elucidated by detailed analysis of spectroscopic data and by comparison with reported data of related derivatives, leading to the structure revision of co-occurring bislatumlides A (5) and B (6) at the C-21 configuration. The absolute configurations of bislatumlides C and E (1 and 3) were determined by TDDFT calculations of their solution ECD spectra, allowing the configurational assignment of the related bislatumlides D and F (2 and 4) and A and B (5 and 6) as well. Bislatumlides A-F (1-6) represent the only biscembranoids formed by the undescribed coupling pattern of Diels-Alder cycloaddition between the Δ1(2) double bond involving an α,β-unsaturated γ-lactone ring as a dienophile group and a trisubstituted conjugated Δ21(34)/Δ35(36)-butadiene moiety. An endo-cycloaddition gave 1, 2, 5, and 6, whereas an exo-cycloaddition produced 3 and 4. This is the first report of exo-addition dicembranoids from marine sources and from nature. Bislatumlides C and E (1, 3) could be used as ECD reference compounds in the determination of absolute configuration for related derivatives.",
author = "Rui Jia and T. Kurt{\'a}n and Attila M{\'a}ndi and Yan, {Xiao Hong} and Wen Zhang and Guo, {Yue Wei}",
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T2 - Structure revision and establishment of their absolute configurations using theoretical calculations of electronic circular dichroism spectra

AU - Jia, Rui

AU - Kurtán, T.

AU - Mándi, Attila

AU - Yan, Xiao Hong

AU - Zhang, Wen

AU - Guo, Yue Wei

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N2 - Four new biscembranoids, bislatumlides C-F (1-4), were isolated from the Hainan soft coral Sarcophyton latum. Their structures were elucidated by detailed analysis of spectroscopic data and by comparison with reported data of related derivatives, leading to the structure revision of co-occurring bislatumlides A (5) and B (6) at the C-21 configuration. The absolute configurations of bislatumlides C and E (1 and 3) were determined by TDDFT calculations of their solution ECD spectra, allowing the configurational assignment of the related bislatumlides D and F (2 and 4) and A and B (5 and 6) as well. Bislatumlides A-F (1-6) represent the only biscembranoids formed by the undescribed coupling pattern of Diels-Alder cycloaddition between the Δ1(2) double bond involving an α,β-unsaturated γ-lactone ring as a dienophile group and a trisubstituted conjugated Δ21(34)/Δ35(36)-butadiene moiety. An endo-cycloaddition gave 1, 2, 5, and 6, whereas an exo-cycloaddition produced 3 and 4. This is the first report of exo-addition dicembranoids from marine sources and from nature. Bislatumlides C and E (1, 3) could be used as ECD reference compounds in the determination of absolute configuration for related derivatives.

AB - Four new biscembranoids, bislatumlides C-F (1-4), were isolated from the Hainan soft coral Sarcophyton latum. Their structures were elucidated by detailed analysis of spectroscopic data and by comparison with reported data of related derivatives, leading to the structure revision of co-occurring bislatumlides A (5) and B (6) at the C-21 configuration. The absolute configurations of bislatumlides C and E (1 and 3) were determined by TDDFT calculations of their solution ECD spectra, allowing the configurational assignment of the related bislatumlides D and F (2 and 4) and A and B (5 and 6) as well. Bislatumlides A-F (1-6) represent the only biscembranoids formed by the undescribed coupling pattern of Diels-Alder cycloaddition between the Δ1(2) double bond involving an α,β-unsaturated γ-lactone ring as a dienophile group and a trisubstituted conjugated Δ21(34)/Δ35(36)-butadiene moiety. An endo-cycloaddition gave 1, 2, 5, and 6, whereas an exo-cycloaddition produced 3 and 4. This is the first report of exo-addition dicembranoids from marine sources and from nature. Bislatumlides C and E (1, 3) could be used as ECD reference compounds in the determination of absolute configuration for related derivatives.

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