https://pubs.rsc.org/en/content/articlepdf/2019/NP/C8NP00092A

Marine natural products.

In studying the evolution of organic chemistry and grasping its essence, one comes quickly to the conclusion that no other type of reaction plays as large a role in shaping this domain of science than carbon-carbon bond-forming reactions. The Grignard, Diels-Alder, and Wittig reactions are but three prominent examples of such processes, and are among those which have undeniably exercised decisive roles in the last century in the emergence of chemical synthesis as we know it today. In the last quarter of the 20th century, a new family of carbon-carbon bond-forming reactions based on transition-metal catalysts evolved as powerful tools in synthesis. Among them, the palladium-catalyzed cross-coupling reactions are the most prominent. In this Review, highlights of a number of selected syntheses are discussed. The examples chosen demonstrate the enormous power of these processes in the art of total synthesis and underscore their future potential in chemical synthesis.

Palladium-catalyzed cross-coupling reactions in total synthesis.

Metal-catalysed C–H bond functionalisation has had a significant impact on how chemists make molecules. Translating the methodological developments to their use in the assembly of complex natural products is an important challenge for the continued advancement of chemical synthesis. In this tutorial review, we describe selected recent examples of how the metal-catalysed C–H bond functionalisation has been able to positively affect the synthesis of natural products.

Recent developments in natural product synthesis using metal-catalysed C–H bond functionalisation

13C NMR spectra of pentacyclic triterpenoids--a compilation and some salient features

Cyanobacterial secondary metabolites have attracted increasing scientific interest due to bioactivity of many compounds in various test systems. Among the known structures, oligopeptides are often found with many congeners sharing conserved substructures, while being highly variable in others. A major part of known oligopeptides are of non-ribosomal origin and can be grouped into classes with conserved structural properties. Thus, the overall structural diversity of cyanobacterial oligopeptides only seemingly suggests an equally high diversity of biosynthetic pathways and respective genes. For each class of peptides, some of which have been found in all major branches of the cyanobacterial evolutionary tree, homologous synthetases and genes can be inferred. This implies that non-ribosomal peptide synthetase genes are a very ancient part of the cyanobacterial genome and presumably have evolved by recombination and duplication events to reach the present structural diversity of cyanobacterial oligopeptides. In addition, peptide synthetases would appear to be an essential part of the cyanobacterial evolution and physiology. The present review presents an overview of the biosynthesis of cyanobacterial peptides and corresponding gene clusters, the structural diversity of structural types and structural variations within peptide classes, and implications for the evolution and plasticity of biosynthetic genes and the potential function of cyanobacterial peptides.

Cyanobacterial peptides – Nature's own combinatorial biosynthesis

Lycopodium alkaloids are unique heterocyclic alkaloids having C 11 N, C 15 N 2 , C 16 N, C 16 N 2 , C 22 N 2 , and C 27 N 3 types from genus Lycopodium and have attracted great interest from biogenetic and biological points of view as well as providing challenging targets for total synthesis This review covered the structure elucidation and biological activity of new Lycopodium alkaloids and total synthesis of some Lycopodium alkaloids reported in the literature from 2004 to July in 2008

The lycopodium alkaloids

Amphidinolides, bioactive macrolides from symbiotic marine dinoflagellates

Three new bicyclic peptides, celogentins A (1), B (2), and C (3), have been isolated together with a known-related peptide, moroidin (4), from the seeds of Celosia argentea, and their structures including absolute stereochemistry were determined by using extensive NMR methods and chemical means. Celogentins A (1), B (2), and C (3) inhibited the polymerization of tubulin, and celogentin C (3) was four times more potent than moroidin (4) in the inhibitory activity. Structure-activity relationship study using moroidin derivatives 5-7 and analogue 8 as well as celogentins A-C (1-3) and moroidin (4) indicates that the bicyclic ring system including unusual non-peptide connections among beta(s)-Leu, Trp, and His residues characteristic of celogentins and moroidin, with ring size and conformations suitable for interaction with tubulin would be important for their biological activity.

Jun'ichi Kobayashi

Papers

The lycopodium alkaloids

Amphidinolides, bioactive macrolides from symbiotic marine dinoflagellates

Celogentins A-C, new antimitotic bicyclic peptides from the seeds of Celosia argentea.

Calyciphyllines A and B, two novel hexacyclic alkaloids from Daphniphyllum calycinum.

Speradine A, a new pentacyclic oxindole alkaloid from a marine-derived fungus Aspergillus tamarii