Carbohydrates to carbocycles: synthesis of the densely functionalized carbocyclic core of tetrodotoxin by radical cyclization of an anhydro sugar precursor

Alonso, Ricardo; Burgey, Christopher S.; Rao, B. Dharma; Vite, Gregory D.; Vollerthun, R.; Zottola, Mark A.; Fraser‐Reid, Bert

doi:10.1021/ja00068a025

Cited by 56 publications

(19 citation statements)

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“…In 1993 synthesis of an advanced TTX intermediate 60 was accomplished by Fraser‐Reid . The inspiration for the work came from Woodward's research, which indicated the retrosynthetic connection between TTX and the apiose derivative .…”

Section: Synthesis Of Ttxmentioning

confidence: 99%

“…Two methods were developed: the first one was based on the 1,3‐dipolar cycloadditions of sugar‐derived ketonitriles while the second rested on radical cyclization of mannopyranose derivative (Scheme ). The utilization of mannopyranose derivatives as starting materials might have been inspired by the previous studies by Fraser‐Reid . The formation of nitrone 251 was followed by an immediate cyclization to isoxazolidine 252 .…”

Section: Synthesis Of Ttxmentioning

confidence: 99%

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Tetrodotoxin: History, Biology, and Synthesis

et al. 2019

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This review provides a comprehensive coverage of the history, biology and chemistry of tetrodotoxin (TTX). It traces the origin of this remarkable molecule all the way back to the ancient Chinese medicine records. The discovery of biological activity, isolation, and a brief overview of structure elucidation are summarized. Next, the biology of TTX is discussed, primarily in the context of its activity in the sodium channels, its anesthetic properties, and its potential use in cancer treatment or drug addiction. Biosynthesis of TTX is covered before the discussion of the total syntheses. All total, formal or partial syntheses are covered but those total syntheses that have been discussed in previous reviews are only briefly summarized. Finally, the synthesis of natural and unnatural derivatives is surveyed, and a conclusion and outlook are provided for this very extensive field of endeavor. To the best of our knowledge the literature coverage is complete up to December 2018.

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Section: Synthesis Of Ttxmentioning

confidence: 99%

Section: Synthesis Of Ttxmentioning

confidence: 99%

Tetrodotoxin: History, Biology, and Synthesis

et al. 2019

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“…Whilst radical cyclisationo nto aC N pbond is feasible, it is about 50 times slowert han its C=Ca nd CCv ariants. [13] This is highlighted by the numerousr eported failed attempts to cyclise onto an itrile group; [14][15][16] although in isolated examples, radical cyclisations ton itriles have been achieved utilisingt ributyltinh ydride, [17][18][19] titanium [20][21][22] and manganese [23] reagents.…”

mentioning

confidence: 99%

Hydrogen Atom Transfer‐Mediated Cyclisations of Nitriles

Turner

Murphy

Hirst

et al. 2018

Chemistry A European J

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Hydrogen atom transfer‐mediated intramolecular C−C coupling reactions between alkenes and nitriles, using PhSiH3 and catalytic Fe(acac)3, are described. This introduces a new strategic bond disconnection for ring‐closing reactions, forming ketones via imine intermediates. Of note is the scope of the reaction, including formation of sterically hindered ketones, spirocycles and fused cyclic systems.

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“…Many approaches have been developed for the synthesis of enantiomerically pure tetrodotoxin among them KEANA'S (532-538), IsOBE'S (539-541) and other approaches(543)(544)(545)(546)(547)(548). Many approaches have been developed for the synthesis of enantiomerically pure tetrodotoxin among them KEANA'S (532-538), IsOBE'S (539-541) and other approaches(543)(544)(545)(546)(547)(548).…”

mentioning

confidence: 99%

Some Aspects of Guanidine Secondary Metabolites

Berlinck

1995

Fortschritte Der Chemie Organischer Naturstoffe / Progress in the Chemistry of Organic Natural Products

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Carbohydrates to carbocycles: synthesis of the densely functionalized carbocyclic core of tetrodotoxin by radical cyclization of an anhydro sugar precursor

Cited by 56 publications

References 0 publications

Tetrodotoxin: History, Biology, and Synthesis

Tetrodotoxin: History, Biology, and Synthesis

Hydrogen Atom Transfer‐Mediated Cyclisations of Nitriles

Some Aspects of Guanidine Secondary Metabolites

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