Lamellarins and Related Pyrrole-Derived Alkaloids from Marine Organisms

Fan, Hui; Peng, Jiangnan; Hamann, Mark T.; Hu, Jin‐Feng

doi:10.1021/cr078199m

Cited by 1,000 publications

(332 citation statements)

References 128 publications

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“…The pyrrole [4][5][6][7] ring is one of the most common skeletal features found in heterocycles and natural products [8][9][10]. Generally, pyrroles possess a broad spectrum of biological activities such as antimicrobial [11], telomerase inhibitory [12], antifungal [13], cardiotonic [14], pheromonal [15], and phytotoxic e ects [16].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of methyl-2-methyl-4-(2-oxo-2-phenylethyl)-5-phenyl-1H-pyrrole-3-carboxylate, C₂₁H₁₉NO₃

Naganagowda

Mahlaka

Meijboom

2016

Zeitschrift Für Kristallographie - New Crystal Structures

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Section: Discussionmentioning

confidence: 99%

Crystal structure of methyl-2-methyl-4-(2-oxo-2-phenylethyl)-5-phenyl-1H-pyrrole-3-carboxylate, C₂₁H₁₉NO₃

Naganagowda

Mahlaka

Meijboom

2016

Zeitschrift Für Kristallographie - New Crystal Structures

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“…The current good possibility that cephalostatin/ritterazine alkaloids inhibit cancer cell growth by affecting a novel molecular target(s), the ongoing total synthetic and SAR challenges, the possibility of locating a marine microorganism source actually responsible for their biosynthesis, and clinical development prospects all suggest that the bis steroidal alkaloids field will become increasingly productive and useful. Among the most promising anti-cancer drug candidates derived from marine invertebrates is the family of lamellarins [37][38][39][40][41]. The lamellarins form a group of more than 50 highly condensed DOPA-derived pyrrole alkaloids that have attracted researchers' interest due to both their structural originality and significant biological properties.…”

Section: Bis-steroidal Pyrazines: Ritterazines and Cephalostatins Pomentioning

confidence: 99%

“…Elegant synthetic routes to lamellarins or their key intermediates have been developed, which afforded sufficient quantities of structurally simplified lamellarin analogs for SAR and other biological studies [39,41]. In an early attempt to correlate the structures of lamellarins with their cytotoxic activities, Quesada et al, observed that an increase in the number of methylations and/or methoxylations appears to cause a decrease in the antitumor activities of the 13 lamellarins tested in their studies [51].…”

Section: Bis-steroidal Pyrazines: Ritterazines and Cephalostatins Pomentioning

confidence: 99%

Alkaloids from Marine Invertebrates as Important Leads for Anticancer Drugs Discovery and Development

et al. 2014

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Abstract:The present review describes research on novel natural antitumor alkaloids isolated from marine invertebrates. The structure, origin, and confirmed cytotoxic activity of more than 130 novel alkaloids belonging to several structural families (indoles, pyrroles, pyrazines, quinolines, and pyridoacridines), together with some of their synthetic analogs, are illustrated. Recent discoveries concerning the current state of the potential and/or development of some of them as new drugs, as well as the current knowledge regarding their modes of action, are also summarized. A special emphasis is given to the role of marine invertebrate alkaloids as an important source of leads for anticancer drug discovery.

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“…Much attention has been focused on highly substituted pyrroles including 3,4-diaryl groups found in a class of alkaloids [1][2][3][4][5][6][7][8][9][10][11][12] ( Fig. 1).…”

mentioning

confidence: 99%

Selective Mono-reduction of Pyrrole-2,5 and 2,4-Dicarboxylates

Yasui

Tsuda

Ohnuki

et al. 2016

CHEMICAL & PHARMACEUTICAL BULLETIN

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Pyrrole-2,5-dicarboxylates were rapidly and selectively reduced to the corresponding mono-alcohol using 3 eq of diisobutylaluminum hydride at 0°C. Pyrrole-2,4-dicarboxylate showed the same reactivity; however, the selectivity decreased with pyrrole-3,4-dicarboxylate. When the nitrogen atom of the pyrrole-2,5-dicarboxylate is protected with a benzyl group, selective mono-reduction does not occur. Considering that furan-2,5-dicarboxylates did not give the corresponding mono-alcohol under the same conditions, the unprotected nitrogen atom of pyrrole apparently plays an important role in this selective mono-reduction. Key words pyrrole dicarboxylate; diisobutylaluminum hydride (DIBAH); selective reductionThe pyrrole ring is an important heterocycle in fields such as medicinal, material and natural product chemistry. Much attention has been focused on highly substituted pyrroles including 3,4-diaryl groups found in a class of alkaloids [1][2][3][4][5][6][7][8][9][10][11][12] ( Fig. 1). We previously reported a synthetic reaction of 3,4-diarylpyrrole-2,5-dicarboxylates from α-diazoesters through a [3,3]-sigmatropic rearrangement of azine, which was also applied to the formal syntheses of polycitones (1) and permethyl storniamide (3b) 13,14) (Chart 1). This reaction is a very concise method but is not directly applicable to the preparation of unsymmetric pyrrole found in Ningalin B (4b) 8) and lamellarins (5).9-12) Such a limitation could be compensated by an efficient desymmetrization. Boger and Patel reported that hydrolysis of pyrrole dicarboxylate 6 gave mono acid 7 in good yield upon treatment with an equivalent of lithium hydroxide at room temperature 15) (Chart 2, example 1). Panda and colleagues applied this method to the desymmetrization of pyrrole dicarboxylate 8 for generating mono acid 9, which was a synthetic intermediate of sapphyrin 16) (example 2). In another case, Yanagisawa and colleagues reported desymmetrization of N-benzyl pyrrole dicarboxylate 10 by treatment with diisobutylaluminum hydride (DIBAH) at a low temperature 17) (example 3). These methods showed acceptable selectivity but needed a very long reaction time. To our knowledge selective mono-reduction of N-non-protected pyrrole dicarboxylates has not been reported so far. We describe here rapid and selective mono-reduction of N-non-protected pyrrole dicarboxylates, which was found during our independent trial to obtain unsymmetric pyrroles.Pyrrole dicarboxylate 12a was subjected to reduction with DIBAH in tetrahydrofuran (THF) at room temperature (Table 1, entry 1). In this case, 12a was completely consumed and mono-alcohol 13a was obtained in 63% yield. Changing solvent to toluene resulted in an increased yield of 13a at 0°C (entry 2). Interestingly, there was almost not reduction of second ester group despite highly excess addition of DIBAH (entry 3).To evaluate the scope of such selectivity, we next carried out reactions of several 3,4-diaryl pyrrole dicarboxylates with DIBAH in toluene at 0°C (Table 2). Thorough and careful experiments ...

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Lamellarins and Related Pyrrole-Derived Alkaloids from Marine Organisms

Cited by 1,000 publications

References 128 publications

Crystal structure of methyl-2-methyl-4-(2-oxo-2-phenylethyl)-5-phenyl-1H-pyrrole-3-carboxylate, C₂₁H₁₉NO₃

Crystal structure of methyl-2-methyl-4-(2-oxo-2-phenylethyl)-5-phenyl-1H-pyrrole-3-carboxylate, C₂₁H₁₉NO₃

Alkaloids from Marine Invertebrates as Important Leads for Anticancer Drugs Discovery and Development

Selective Mono-reduction of Pyrrole-2,5 and 2,4-Dicarboxylates

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Lamellarins and Related Pyrrole-Derived Alkaloids from Marine Organisms

Cited by 1,000 publications

References 128 publications

Crystal structure of methyl-2-methyl-4-(2-oxo-2-phenylethyl)-5-phenyl-1H-pyrrole-3-carboxylate, C21H19NO3

Crystal structure of methyl-2-methyl-4-(2-oxo-2-phenylethyl)-5-phenyl-1H-pyrrole-3-carboxylate, C21H19NO3

Alkaloids from Marine Invertebrates as Important Leads for Anticancer Drugs Discovery and Development

Selective Mono-reduction of Pyrrole-2,5 and 2,4-Dicarboxylates

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Product

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Crystal structure of methyl-2-methyl-4-(2-oxo-2-phenylethyl)-5-phenyl-1H-pyrrole-3-carboxylate, C₂₁H₁₉NO₃

Crystal structure of methyl-2-methyl-4-(2-oxo-2-phenylethyl)-5-phenyl-1H-pyrrole-3-carboxylate, C₂₁H₁₉NO₃