title: Structure and Absolute Configuration of Jurassic Polyketide-Derived Spiroborate Pigments Obtained from Microgram Quantities.
abstract: Complete structural elucidation of natural products is often challenging due to structural complexity and limited availability. This is true for present-day secondary metabolites, but even more for exceptionally preserved secondary metabolites of ancient organisms that potentially provide insights into the evolutionary history of natural products. Here, we report the full structure and absolute configuration of the borolithochromes, enigmatic boron-containing pigments from a Jurassic putative red alga, from samples of less than 50 μg using microcryoprobe NMR, circular dichroism spectroscopy, and density functional theory calculations and reveal their polyketide origin. The pigments are identified as spiroborates with two pentacyclic sec-butyl-trihydroxy-methyl-benzo[gh]tetraphen-one ligands and less-substituted derivatives. The configuration of the sec-butyl group is found to be (S). Because the exceptional benzo[gh]tetraphene scaffold is otherwise only observed in the recently discovered polyketide clostrubin from a present-day Clostridium bacterium, the Jurassic borolithochromes now can be unambiguously linked to the modern polyketide, providing evidence that the fossil pigments are almost originally preserved secondary metabolites and suggesting that the pigments in fact may have been produced by an ancient bacterium. The borolithochromes differ fundamentally from previously described boronated polyketides and represent the first boronated aromatic polyketides found so far. Our results demonstrate the potential of microcryoprobe NMR in the analysis of previously little-explored secondary metabolites from ancient organisms and reveal the evolutionary significance of clostrubin-type polyketides.
authors.affiliation: Department of Geobiology, Geoscience Centre, University of Göttingen , Goldschmidtstraße 3, 37077 Göttingen, Germany.
authors.forename: Klaus
authors.initials: K
authors.lastname: Wolkenstein
authors.affiliation: Department of NMR Based Structural Biology, Max Planck Institute for Biophysical Chemistry , Am Fassberg 11, 37077 Göttingen, Germany.
authors.forename: Han
authors.initials: H
authors.lastname: Sun
authors.affiliation: Institute of Organic Chemistry, University of Linz , Altenbergerstraße 69, 4040 Linz, Austria.
authors.forename: Heinz
authors.initials: H
authors.lastname: Falk
authors.affiliation: Department of NMR Based Structural Biology, Max Planck Institute for Biophysical Chemistry , Am Fassberg 11, 37077 Göttingen, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Griesinger
mesh_terms: D053000:Analytic Sample Preparation Methods; D004396:Coloring Agents / Q000737:chemistry*; D015394:Molecular Structure; D036103:Nanotechnology; D010163:Paleontology; D061065:Polyketides / Q000737:chemistry*; D000461:Rhodophyta / Q000737:chemistry
chemical_list: D004396:Coloring Agents; D061065:Polyketides; C000609104:borolithochrome G