Total Synthesis of the Marine Alkaloids (−)-Lepadins A, B, and C Based on Stereocontrolled Intramolecular Acylnitroso-Diels−Alder Reaction

Ozawa, Tetsuji; Kibayashi, Chihiro

doi:10.1021/jo001589n

Cited by 76 publications

(41 citation statements)

References 27 publications

(28 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…508 A new member of the tunichrome family of modified peptides, tunichrome Sp-1 668 was isolated from the hemocytes of Styela plicata, collected in Mission Bay, California. 516 Lepadins F-H 672-674 were reported from extracts of the ascidian Aplidium tabascum collected from Swains Reef, Great Barrier Reef. The ascidian Didemnum molle, collected at Ibo Island north of Mozambique, was the source of the cycloheptapeptide cyclodidemnamide B 669.…”

Section: Tunicates (Ascidians)mentioning

confidence: 99%

Marine natural products

et al. 2004

View full text Add to dashboard Cite

This review covers the literature published in 2002 for marine natural products, with 579 citations (413 for the period January to December 2002) referring to compounds isolated from marine microorganisms and phytoplankton, green algae, brown algae, red algae, sponges, coelenterates, bryozoans, molluscs, tunicates and echinoderms. The emphasis is on new compounds (677 for 2002), together with their relevant biological activities, source organisms and country of origin. Syntheses that lead to the revision of structures or stereochemistries have been included (114), including any first total syntheses of a marine natural product.

show abstract

Section: Tunicates (Ascidians)mentioning

confidence: 99%

Marine natural products

et al. 2004

View full text Add to dashboard Cite

show abstract

“…This synthesis also proved the absolute stereochemistry of this natural product. The second and even longer tour de force synthesis of lepadin B (2) came from the Kibayashi group in 2000 [23,24]. The synthesis started with the S-malic acid derived chiral aldehyde 39, which was elaborated to compound 40 in four steps via two sequential olefination reactions.…”

Section: Synthetic Effortsmentioning

confidence: 99%

“…Intramolecular aldol cyclization of compound 24 followed by oxidation by pyridinium dichromate (PDC) and methylation gave decahydroquinoline 47 as a single diastereomer [23,24]. Elimination of the hydroxyl group followed by tetrabutylammonium fluoride (TBAF) mediated deprotection and iterative epimerization of the stereocenter at position 5 produced intermediate 48.…”

Section: Synthetic Effortsmentioning

confidence: 99%

Stereocontrolled construction of decahydro quinoline ring systems: the case of lepadin alkaloids (Review)

Pelšs

Koskinen

2013

Chem Heterocycl Comp

View full text Add to dashboard Cite

In this review the marine derived decahydroquinoline alkaloid chemistry and biology is described. A proposal is made for the biosynthetic relationships between acyclic and cyclic C-18 amino alcohol natural products.Keywords: amino alcohols, decahydroquinolines, asymmetric synthesis, biosynthesis, total synthesis. Decahydroquinoline (DHQ) alkaloids are unique natural products that can be divided into three distinct sets. The first group (more than 50 members) of these alkaloids are simple 2,5-disubstituted DHQs isolated from dart poison frogs and ants with the parent member being alkaloid cis-195A, also known as pumiliotoxin C [1]. These diverse cis-or trans-fused decahydroquinolines are equipped with various short alkyl and alkenyl side chains. The structurally related but biologically different lepadins 1-8 (Fig. 1) are on the other hand marine alkaloids isolated from three distinct ascidians: Clavelina lepadiformis (found in the North Sea), Didemnum, and Aplidium tabascum (both found in the Great Barrier Reef) [2][3][4][5]. The third group consists of more complex polycyclic alkaloids that besides the DHQ ring system, can contain several other heterocyclic ring systems fused into one molecule. Representative members of this group are gephyrotoxin and Lycopodium alkaloids [6,7]. This review will focus solely on the second group of DHQ alkaloids which, as distinct from the other two groups of DHQ-containing alkaloids, have not been reviewed in full so far [8]. Lepadin alkaloids differ from dendrobatin frog alkaloids in additional oxygenation at position 3, where the substituent may be a hydroxy or acyloxy group, as well as having eight-carbon long side chains of variable oxidation level at position 5 of the DHQ ring. There are three stereochemical groups of lepadins, each derived from distinct tunicate species (Fig. 1). Lepadin F is an exception, being present in both ascidians from the Great Barrier Reef. Lepadins possess some interesting biological activities: lepadins A and B -cytotoxicity against cancer cell lines, lepadins D-F -antiplasmodal and antitrypanosomal activity. Lately, lepadin B together with pictamine was found to block neuronal nicotinic acetylcholine receptors α4β2 and α7. However, the availability of only small quantities of these natural products has precluded further studies on the development into potential leads for nicotinic based therapies [9].

show abstract

“…87 The total synthesis of (-)-lepadin B 191 is a good illustration of Kibayashi's methodology. 88,89 The lepadins are marine natural products that have been found in the flatworm Prostheceraeus villatus and its tunicate prey Clavenia lepadiformis. They display significant cytotoxicity against human cancer cell lines.…”

Section: Nitroso Dienophilesmentioning

confidence: 99%

Cycloadditions with StereoselectiveCNBond Formation in Total Syntheses

Vincent

2013

Stereoselective Synthesis of Drugs and Natural Products

View full text Add to dashboard Cite

Cycloadditions reactions are very efficient tools for the constructions of multiple bonds in one step and are therefore methods of choice for the total synthesis of natural products and drugs. The use of a terminal nitrogen containing partner allows for the stereoselective formations of a CN bond. Because of the vast number of nitrogen containing compounds available, this field has found a widespread interest in total synthesis. This chapter will cover the cycloadditions in which a CN bond is formed. It will be devoted to the description of [2+2], [3+2], [3+3], [4+2], and [2+2+2] processes that are key steps in total synthesis with imine, nitroso, azo, isocyanate, azomethine imine, azide, or azadiene reagents. A discussion of regioselectivity, diastereoselectivity, and enantioselectivity issues will be provided for each reaction.

show abstract

Total Synthesis of the Marine Alkaloids (−)-Lepadins A, B, and C Based on Stereocontrolled Intramolecular Acylnitroso-Diels−Alder Reaction

Cited by 76 publications

References 27 publications

Marine natural products

Marine natural products

Stereocontrolled construction of decahydro quinoline ring systems: the case of lepadin alkaloids (Review)

Cycloadditions with StereoselectiveCNBond Formation in Total Syntheses

Contact Info

Product

Resources

About