A New Synthetic Route to the Skeleton of Saxitoxin, a Naturally Occurring Blocker of Voltage-Gated Sodium Channels

Sawayama, Yusuke; Nishikawa, Toshio

doi:10.5059/yukigoseikyokaishi.70.1178

Cited by 18 publications

(9 citation statements)

References 53 publications

(9 reference statements)

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“…As the new conditions are very mild, this novel transformation should be widely applicable in combination with the bromocyclization procedures developed in this laboratory. [1] Application of this procedure to the syntheses of other natural products and transformation of the gem-dibromomethylene unit to functional groups other than ketone are currently under way in this laboratory.…”

Section: Discussionmentioning

confidence: 99%

“…Highly functionalized compounds 1 and 4 were inert under the precedent conditions using silver cation‐mediated hydrolysis, whereas attempted hydrolysis of the simpler compounds, such as 12 and 14 , provided the alkenylbromide (through elimination of HBr) as the major product. As the new conditions are very mild, this novel transformation should be widely applicable in combination with the bromocyclization procedures developed in this laboratory 1. Application of this procedure to the syntheses of other natural products and transformation of the gem ‐dibromomethylene unit to functional groups other than ketone are currently under way in this laboratory.…”

Section: Discussionmentioning

confidence: 99%

“…In the course of our synthetic studies on saxitoxin, [1] aw ellknown paralytic shellfish poison, we incidentally found an ew transformation of a gem-dibromomethylene to the corresponding enol acetate, as shown in Scheme 1. [2] When we attempted acetylation of compound 1,w hich was synthesized by ac ascade bromocyclization developed in this laboratory, [3] under conventional conditions (acetic anhydride and triethylamine in dichloromethane at room temperature), enol acetate 2 was observed as an unstablep roduct.T his unstable product was isolated as alcohol 3 in 64 %y ield after successive treatment with NaBH 4 and K 2 CO 3 in methanol.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Unexpected Metal‐Free Transformation of gem‐Dibromomethylenes to Ketones under Acetylation Conditions

Kimura

Sawayama

Nakazaki

et al. 2015

Chemistry An Asian Journal

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Unexpected Metal‐Free Transformation of gem‐Dibromomethylenes to Ketones under Acetylation Conditions

Kimura

Sawayama

Nakazaki

et al. 2015

Chemistry An Asian Journal

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“…42,266-292 They first accomplished the synthesis of 5,11-dideoxytetrodotoxin in 1999. 275,277,286 They then achieved the syntheses of 8,11-dideoxytetrodotoxin 279,282 and 11-deoxytetrodotoxin ( 3a ), 278 in 2002.…”

Section: The Saxitoxin/tetrodotoxin Alkaloidsmentioning

confidence: 99%

“…290-292 Aziridine 232 , prepared from ( S )-Garner's aldehyde, was transformed into mesylate 233 (Fig. 41).…”

Section: The Saxitoxin/tetrodotoxin Alkaloidsmentioning

confidence: 99%

Syntheses of cyclic guanidine-containing natural products

Chen

2015

Tetrahedron

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Naturally occurring guanidine derivatives frequently display medicinally useful properties. Among them, the higher order pyrrole-imidazole alkaloids, the dragmacidins, the crambescidins/batzelladines, and the saxitoxins/tetradotoxins have stimulated the development of many new synthetic methods over the past decades. We provide here an overview of the syntheses of these cyclic guanidine-containing natural products.

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Synthesis of 5‐ and 8‐Deoxytetrodotoxin

Satake

Adachi

Tokoro

et al. 2014

Chemistry An Asian Journal

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Tetrodotoxin, a toxic principle of puffer fish intoxication, is one of the most famous marine natural products owing to its complex structure and potent biological activity, which leads to fatal poisoning. Continuous synthetic studies on tetrodotoxin and its analogues to elucidate biologically interesting issues associated with tetrodotoxin have led to the development of versatile routes for a variety of tetrodotoxin derivatives. With the aim of investigating the structure-activity relationship of tetrodotoxin with voltage-gated sodium channels, this study describes the first total syntheses of 5-deoxytetrodotoxin, a natural analogue of tetrodotoxin, and 8-deoxytetrodotoxin, an unnatural analogue, from a newly designed, versatile intermediate in an efficient manner. An estimation of the biological activities of these compounds reveals the importance of the hydroxy groups at the C-5 and C-8 positions on the inhibition of voltage-gated sodium channels.

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A New Synthetic Route to the Skeleton of Saxitoxin, a Naturally Occurring Blocker of Voltage-Gated Sodium Channels

Cited by 18 publications

References 53 publications

Unexpected Metal‐Free Transformation of gem‐Dibromomethylenes to Ketones under Acetylation Conditions

Unexpected Metal‐Free Transformation of gem‐Dibromomethylenes to Ketones under Acetylation Conditions

Syntheses of cyclic guanidine-containing natural products

Synthesis of 5‐ and 8‐Deoxytetrodotoxin

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