Total Synthesis of Chatancin

Aigner, Josef; Gössinger, Edda; Kählig, Hanspeter; Menz, Georg; Pflugseder, Karin

doi:10.1002/(sici)1521-3773(19980904)37:16<2226::aid-anie2226>3.0.co;2-h

Cited by 23 publications

(1 citation statement)

References 8 publications

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“…The intriguing terpene skeleton of 1 is suggestive of potential cembranoid biosynthetic origins (see 18 ), and its complex polycyclic ring system is proposed to arise from a transannular [4 + 2] cycloaddition between an alkene and a pyran, furan, or pyrylium-type (see 17 ) diene . The latter, pyrylium-based pathway is favored energetically according to calculations by Tantillo and co-workers. , Inspired by the unique polycyclic framework and bioactivity of chatancin ( 1 ), the groups of Gössinger, Deslongchamps, Maimone, and Ding have each reported distinct total syntheses.…”

Section: Total Synthesis Of Chatancinmentioning

confidence: 99%

Syntheses of Complex Terpenes from Simple Polyprenyl Precursors

et al. 2020

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Conspectus From structure elucidation and biogenesis to synthetic methodology and total synthesis, terpene natural products have profoundly influenced the development of organic chemistry. Moreover, their myriad functional attributes range from fragrance to pharmaceuticals and have had great societal impact. Ruzicka’s formulation of the “biogenetic isoprene rule,” a Nobel Prize winning discovery now over 80 years old, allowed for identification of higher order terpene (aka “isoprenoid”) structures from simple five-carbon isoprene fragments. Notably, the isoprene rule still holds pedagogical value to students of organic chemistry today. Our laboratory has completed syntheses of over two dozen terpene and meroterpene structures to date, and the isoprene rule has served as a key pattern recognition tool for our synthetic planning purposes. At the strategic level, great opportunity exists in finding unique and synthetically simplifying ways to connect the formal C5 isoprene fragments embedded in terpenes. Biomimetic cationic polyene cyclizations represent the earliest incarnation of this idea, which has facilitated expedient routes to certain terpene polycycle classes. Nonetheless, a large swath of terpene chemical space remains inaccessible using this approach. In this Account, we describe strategic insight into our endeavors in terpene synthesis published over the last five years. We show how biosynthetic understanding, combined with a desire to utilize abundant and inexpensive [C5] n building blocks, has led to efficient, abiotic syntheses of multiple complex terpenes with disparate ring systems. Informed by nature, but unconstrained by its processes, our synthetic assembly exploits chemical reactivity across diverse reaction typesincluding radical, anionic, pericyclic, and metal-mediated transformations. First, we detail an eight-step synthesis of the cembrane diterpene chatancin from dihydrofarnesal using a bioinspiredbut not -mimeticcycloaddition. Next, we describe the assembly of the antimalarial cardamom peroxide using a polyoxygenation cascade to fuse multiple units of molecular oxygen onto a dimeric skeleton. This three-to-four-step synthesis arises from (−)-myrtenal, an inexpensive pinene oxidation product. We then show how a radical cyclization cascade can forge the hallmark cyclooctane ring system of the complex sesterterpene 6-epi-ophiobolin N from two simple polyprenyl precursors, (−)-linalool and farnesol. To access the related, more complex metabolite 6-epi-ophiobolin A, we exploited the plasticity of our synthetic route and found that use of geraniol (C10) rather than farnesol (C15) gave us the flexibility needed to address the additional oxidation found in this congener. Following this work, we describe two strategies to access several guaianolide sesquiterpenes. Retrosynthetic disconnection to monoterpenes, carvone or (−)-linalool, coupled with a powerful allylation strategy allowed us to address guaianolides with disparate stereochemical motifs. Finally, we examine a semisynthetic approach to...

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Section: Total Synthesis Of Chatancinmentioning

confidence: 99%

Syntheses of Complex Terpenes from Simple Polyprenyl Precursors

et al. 2020

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1,2,3,4-Tetrachloro-5,5-dimethoxy-cyclopenta-1,3-diene: Diels Alder Reactions and Applications of the Products Formed

Khan

Prabhudas

2000

J. prakt. Chem.

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Cnidaria and Ctenophora–2

Kornprobst

2014

Encyclopedia of Marine Natural Products

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The article contains sections titled: Membrane Constituents and Secondary Metabolites of Hexacorallia (Anthozoa) Fatty Acids, Oxylipins, and Acetylenic Derivatives Sterols and Ecdysteroids Terpenes Carotenoids of Sea Anemones Aromatic Derivatives Ceramides and Lipidic α‐Amino Acids Examples of Nitrogenous Pigments: Zoanthoxanthins and Calliactine Palytoxins ( PTXs ) Mycosporines Betaines, Phosphobetaines, Purines, and Other Nitrogen‐Containing Derivatives Zoanthamine Alkaloids Cytolysins, Neuropeptides, and Other Venoms of Sea Anemones Venoms and Other Metabolites of Medusozoa Some Data on the Cubozoa and Other Jellyfish Bioluminescence of Jellyfish and Other Cnidaria Some Results on the Secondary Metabolites of Other Hydrozoa Ctenophora

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Total Synthesis of Chatancin

Cited by 23 publications

References 8 publications

Syntheses of Complex Terpenes from Simple Polyprenyl Precursors

Syntheses of Complex Terpenes from Simple Polyprenyl Precursors

1,2,3,4-Tetrachloro-5,5-dimethoxy-cyclopenta-1,3-diene: Diels Alder Reactions and Applications of the Products Formed

Cnidaria and Ctenophora–2

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