A Series of Chiral Polybrominated Biindoles from the Marine Blue-Green Alga Rivularia firma. Application of 13C NMR Spin-Lattice Relaxation Data and 13C-1H Coupling Constants to Structure Elucidation

Raymond S. Norton, Robert J. Wells

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Abstract

Six novel polybrominated biindole derivatives have been isolated from the marine blue-green alga Rivularia firma: 2,2′,5,5′-tetrabromo-3,3′-bi-1H-indole (1), (+)-2,3′,5,5′-tetrabromo-7′-methoxy-3,4′-bi-1H-indole (2), (+)-3′,5,5′-tribromo-7′-methoxy-3,4′-bi-1H-indole (3), (+)-2,5,5′-tribromo-7′-methoxy-3,4′-bi-1H-indole (4), (−)-3,3′,5,5′-tetrabromo-7′-methoxy-1,4′-bi-1H-indole (5), and (+)-2,2′,3,4′,5,5′-hexabromo-1,3′-bi-1H-indole (6). Structures were solved by analysis of 1H and 13C chemical shifts, 13C-1H coupling constants, and 13C spin-lattice relaxation data (at 15.04 MHz). The contributions of 13C-1H dipolar interactions to the spin-lattice relaxation times (T1) of quaternary carbons were determined from measured T1 and nuclear Overhauser enhancement values and then used to estimate the numbers of protons two bonds removed from each quaternary carbon. This information was used in structure determination as well as for resonance assignments. Spin-lattice relaxation data were also used to identify brominated carbons. The biindoles 2–6 are optically active and are therefore new representatives of a very small number of natural products in which chirality is due solely to restricted rotation.

Original languageEnglish
Pages (from-to)3628-3635
Number of pages8
JournalJournal of the American Chemical Society
Volume104
Issue number13
DOIs
Publication statusPublished - 1982
Externally publishedYes

Cite this

@article{dde3c595eb034f77b1dd01fa493496ad,
title = "A Series of Chiral Polybrominated Biindoles from the Marine Blue-Green Alga Rivularia firma. Application of 13C NMR Spin-Lattice Relaxation Data and 13C-1H Coupling Constants to Structure Elucidation",
abstract = "Six novel polybrominated biindole derivatives have been isolated from the marine blue-green alga Rivularia firma: 2,2′,5,5′-tetrabromo-3,3′-bi-1H-indole (1), (+)-2,3′,5,5′-tetrabromo-7′-methoxy-3,4′-bi-1H-indole (2), (+)-3′,5,5′-tribromo-7′-methoxy-3,4′-bi-1H-indole (3), (+)-2,5,5′-tribromo-7′-methoxy-3,4′-bi-1H-indole (4), (−)-3,3′,5,5′-tetrabromo-7′-methoxy-1,4′-bi-1H-indole (5), and (+)-2,2′,3,4′,5,5′-hexabromo-1,3′-bi-1H-indole (6). Structures were solved by analysis of 1H and 13C chemical shifts, 13C-1H coupling constants, and 13C spin-lattice relaxation data (at 15.04 MHz). The contributions of 13C-1H dipolar interactions to the spin-lattice relaxation times (T1) of quaternary carbons were determined from measured T1 and nuclear Overhauser enhancement values and then used to estimate the numbers of protons two bonds removed from each quaternary carbon. This information was used in structure determination as well as for resonance assignments. Spin-lattice relaxation data were also used to identify brominated carbons. The biindoles 2–6 are optically active and are therefore new representatives of a very small number of natural products in which chirality is due solely to restricted rotation.",
author = "Norton, {Raymond S.} and Wells, {Robert J.}",
year = "1982",
doi = "10.1021/ja00377a014",
language = "English",
volume = "104",
pages = "3628--3635",
journal = "Journal of the American Chemical Society",
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publisher = "ACS Publications",
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T1 - A Series of Chiral Polybrominated Biindoles from the Marine Blue-Green Alga Rivularia firma. Application of 13C NMR Spin-Lattice Relaxation Data and 13C-1H Coupling Constants to Structure Elucidation

AU - Norton, Raymond S.

AU - Wells, Robert J.

PY - 1982

Y1 - 1982

N2 - Six novel polybrominated biindole derivatives have been isolated from the marine blue-green alga Rivularia firma: 2,2′,5,5′-tetrabromo-3,3′-bi-1H-indole (1), (+)-2,3′,5,5′-tetrabromo-7′-methoxy-3,4′-bi-1H-indole (2), (+)-3′,5,5′-tribromo-7′-methoxy-3,4′-bi-1H-indole (3), (+)-2,5,5′-tribromo-7′-methoxy-3,4′-bi-1H-indole (4), (−)-3,3′,5,5′-tetrabromo-7′-methoxy-1,4′-bi-1H-indole (5), and (+)-2,2′,3,4′,5,5′-hexabromo-1,3′-bi-1H-indole (6). Structures were solved by analysis of 1H and 13C chemical shifts, 13C-1H coupling constants, and 13C spin-lattice relaxation data (at 15.04 MHz). The contributions of 13C-1H dipolar interactions to the spin-lattice relaxation times (T1) of quaternary carbons were determined from measured T1 and nuclear Overhauser enhancement values and then used to estimate the numbers of protons two bonds removed from each quaternary carbon. This information was used in structure determination as well as for resonance assignments. Spin-lattice relaxation data were also used to identify brominated carbons. The biindoles 2–6 are optically active and are therefore new representatives of a very small number of natural products in which chirality is due solely to restricted rotation.

AB - Six novel polybrominated biindole derivatives have been isolated from the marine blue-green alga Rivularia firma: 2,2′,5,5′-tetrabromo-3,3′-bi-1H-indole (1), (+)-2,3′,5,5′-tetrabromo-7′-methoxy-3,4′-bi-1H-indole (2), (+)-3′,5,5′-tribromo-7′-methoxy-3,4′-bi-1H-indole (3), (+)-2,5,5′-tribromo-7′-methoxy-3,4′-bi-1H-indole (4), (−)-3,3′,5,5′-tetrabromo-7′-methoxy-1,4′-bi-1H-indole (5), and (+)-2,2′,3,4′,5,5′-hexabromo-1,3′-bi-1H-indole (6). Structures were solved by analysis of 1H and 13C chemical shifts, 13C-1H coupling constants, and 13C spin-lattice relaxation data (at 15.04 MHz). The contributions of 13C-1H dipolar interactions to the spin-lattice relaxation times (T1) of quaternary carbons were determined from measured T1 and nuclear Overhauser enhancement values and then used to estimate the numbers of protons two bonds removed from each quaternary carbon. This information was used in structure determination as well as for resonance assignments. Spin-lattice relaxation data were also used to identify brominated carbons. The biindoles 2–6 are optically active and are therefore new representatives of a very small number of natural products in which chirality is due solely to restricted rotation.

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U2 - 10.1021/ja00377a014

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