Tetrodotoxin (TTX, 1) is a potent neurotoxin causing fatal food poisoning in human. This toxin is wide-distributed amongst marine animals and terrestrial amphibian. TTX has complex structure consisting of a 2,4-dioxaadamantane skeleton and a cyclic guanidine. The biosynthesis of TTX is enigmatic despite its interest in the biogenetic mechanism constructing the unique structure and high importance in the aspect of food hygiene. The genes and enzymes related to the biosynthesis of TTX have not been elucidated. As an approach to this mystery, we have identified a number of natural TTX analogues and its possible biosynthetic intermediates from the toxic animals, which provide the hints of its pathways.1
In case of newts, we discovered TTX analogues (4­–6)2–4, and cyclic guanidino compounds (7­–11)3–5 using a mass spectrometry (MS)-guided screening method. Compounds 6­–11 possess bicyclic or tricyclic structures consisting of a monoterpene skeleton and a six-membered cyclic guanidine. Recently, novel skeletal tricyclic guanidino compounds (2 and 3) were found, and these structures were elucidated via NMR analysis including long range-HSQMBC.6 Based on the structures of the series of TTX analogues and cyclic guanidino compounds in tetrodotoxin bearing newts, we proposed the biosynthetic/shunt pathways of TTX in the terrestrial organisms derived from monoterpene, that produce the structurally diversified chemicals.
References
(1) Ueyama, N.; and Yotsu-Yamashita, M.; et al. Chem. - Eur. J. 2018, 24, 7250.
(2) Kudo, Y.; Yotsu-Yamashita, M.; et al. Angew. Chem., Int. Ed. 2014, 53, 14546.
(3) Kudo, Y.; Yotsu-Yamashita, M. J. Nat. Prod. 2019, 82, 1656.
(4) Kudo, Y.; Yotsu-Yamashita, M.; et al. J. Nat. Prod. 2020, 83, 2706.
(5) Kudo, Y.; Yotsu-Yamashita, M.; et al. Angew. Chem., Int. Ed. 2016, 55, 8728.
(6) Kudo, Y.; Yotsu-Yamashita, M.; et al. Org. Lett. 2021, 23, 3513.

Identification of New Analogues and Putative Biosynthetic Intermediates/Shunts of Tetrodotoxin from Toxic Newts

In order to view the entire gallery of posters, videos, and other materials, please click "Submissions" below.

To find the Q&A for each poster category, please click "Sessions" below. To ask a question, simply click on the category session; they are organized alphabetically by title. After clicking, you'll see a list of video presentations in the list to the right. Below each video area, you'll see a section entitled 'Q&A for this presentation:'. Here you'll be able to post questions to the authors. They'll be notified, and you'll also be notified when they reply to your question. You can expect that notification by email, and you'll find the author's response here. 

ACS Publications Symposium

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.