Synthesis of (±)-Aureol by Bioinspired Rearrangements

Rosales, Antonio; Muñoz-Bascón, Juan; Roldán-Molina, Esther; Rivas-Bascón, Nazaret; Padial, Natalia M.; Rodriguez-Maecker, Román; Rodrı́guez-Garcı́a, Ignacio; Oltra, J. Enrique

doi:10.1021/jo502841u

Cited by 45 publications

(35 citation statements)

References 27 publications

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“…Physical and spectroscopic properties of synthetic (±)-aureol ((±)-1) matched those previously reported for the natural compound [2]. Thus, the synthesis of (±)-aureol ((±)-1) from (±)-albicanol (5) was completed in only seven steps and a global 28% yield, substantially improving the synthetic procedures previously published [11][12][13][14][15][16][17][18][19][20]. Moreover, a simple epimerization of aureol (1) to 5-epi-aureol (11) has The synthesis of (±)-aureol ((±)-1) (Scheme 2) used as starting material (±)-albicanol (5), which was prepared through Cp 2 TiCl-catalyzed radical cascade cyclization of epoxy-farnesyl acetate, as previously reported by us and others [24,25].…”

Section: Resultssupporting

confidence: 64%

“…As a continuation of our research on the synthesis of marine natural bioactive compounds [18,[21][22][23], we have developed a new concise route for the synthesis of tetracyclic meroterpenoids. In this new synthetic route, aureol (1) is the key intermediate from which other tetracyclic meroterpenoids, such as 2, 3 and 4, can be easily synthesized by simple functional modification of its aromatic ring.…”

Section: Resultsmentioning

confidence: 99%

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A Concise Route for the Synthesis of Tetracyclic Meroterpenoids: (±)-Aureol Preparation and Mechanistic Interpretation

et al. 2020

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A new concise general methodology for the synthesis of different tetracyclic meroterpenoids is reported: (±)‑aureol (1), the key intermediate of this general route. The synthesis of (±)‑aureol (1) was achieved in seven steps (28% overall yield) from (±)‑albicanol. The key steps of this route include a C–C bond-forming reaction between (±)‑albicanal and a lithiated arene unit and a rearrangement involving 1,2‑hydride and 1,2-methyl shifts promoted by BF3•Et2O as activator and water as initiator.

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Section: Resultssupporting

confidence: 64%

Section: Resultsmentioning

confidence: 99%

A Concise Route for the Synthesis of Tetracyclic Meroterpenoids: (±)-Aureol Preparation and Mechanistic Interpretation

et al. 2020

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“…In contrast to these approaches, in which the crucial stereochemistry of the decalin ring system is set in a stepwise manner, Rosales applied a very elegant Ti III ‐mediated reductive epoxide cyclization cascade to construct 11 . In addition, Cramer reported a ruthenium(III)‐catalyzed domino cyclization of a model substrate to access the tetracyclic core of the aureol family of natural products …”

Section: Introductionmentioning

confidence: 99%

“…As previous work has shown that formation of the tetracyclic ring system via biomimetic polyene cyclization and Wagner–Meerwein shifts can only occur in a stepwise manner in the laboratory, we were searching for a strategy to mimic the highly organized environment of an enzymatic active site more efficiently. In order to overcome the current inability of synthetic methodology to mimic these two independently occurring events in a single flask, we recently investigated the cyclization of a well‐elaborated polyene .…”

Section: Introductionmentioning

confidence: 99%

Evolution of a Polyene Cyclization Cascade for the Total Synthesis of (−)‐Cyclosmenospongine

Speck

Magauer

2016

Chemistry A European J

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We report a full account on the development of a unique cationic polyene cyclization for the total synthesis of the tetracyclic meroterpenoid (−)‐cyclosmenospongine. A highly convergent three‐component coupling strategy enabled rapid access to individual cyclization precursors that were tested for their reactivity. The successful transformation generates three rings and sets four consecutive stereocenters in a single operation proceeding in a highly efficient manner to give exclusively the trans‐decalin framework. In addition, we found that the enol ether geometry and the relative configuration of C3 and C8 are crucial for the success of the polyene cyclization.

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“…A concise synthesis of 5,6-dibromotryptamine has been accomplished, starting from the intermediate 5,6-dibromoindole-3-carbaldehyde [ 89 ]. First synthesis of the chiral paureol had been described before, starting from (+)-arenarol [ 90 ], while other syntheses have been recently reported [ 91 , 92 ].…”

Section: Porifera Involved In the Biosynthesis Of Cytotoxic Metabomentioning

confidence: 99%

Cytotoxic Compounds Derived from Marine Sponges. A Review (2010–2012)

et al. 2017

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This extensive review covers research published between 2010 and 2012 regarding new compounds derived from marine sponges, including 62 species from 60 genera belonging to 33 families and 13 orders of the Demospongia class (Porifera). The emphasis is on the cytotoxic activity that bioactive metabolites from sponges may have on cancer cell lines. At least 197 novel chemical structures from 337 compounds isolated have been found to support this work. Details on the source and taxonomy of the sponges, their geographical occurrence, and a range of chemical structures are presented. The compounds discovered from the reviewed marine sponges fall into mainly four chemical classes: terpenoids (41.9%), alkaloids (26.2%), macrolides (8.9%) and peptides (6.3%) which, along with polyketides, sterols, and others show a range of biological activities. The key sponge orders studied in the reviewed research were Dictyoceratida, Haplosclerida, Tetractinellida, Poecilosclerida, and Agelasida. Petrosia, Haliclona (Haplosclerida), Rhabdastrella (Tetractinellida), Coscinoderma and Hyppospongia (Dictyioceratida), were found to be the most promising genera because of their capacity for producing new bioactive compounds. Several of the new compounds and their synthetic analogues have shown in vitro cytotoxic and pro-apoptotic activities against various tumor/cancer cell lines, and some of them will undergo further in vivo evaluation.

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Synthesis of (±)-Aureol by Bioinspired Rearrangements

Cited by 45 publications

References 27 publications

A Concise Route for the Synthesis of Tetracyclic Meroterpenoids: (±)-Aureol Preparation and Mechanistic Interpretation

A Concise Route for the Synthesis of Tetracyclic Meroterpenoids: (±)-Aureol Preparation and Mechanistic Interpretation

Evolution of a Polyene Cyclization Cascade for the Total Synthesis of (−)‐Cyclosmenospongine

Cytotoxic Compounds Derived from Marine Sponges. A Review (2010–2012)

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