34272-51-0Relevant academic research and scientific papers
Total Synthesis of (?)-Histrionicotoxin through a Stereoselective Radical Translocation–Cyclization Reaction
Sato, Manabu,Azuma, Hiroki,Daigaku, Akihiro,Sato, Sota,Takasu, Kiyosei,Okano, Kentaro,Tokuyama, Hidetoshi
supporting information, p. 1087 - 1091 (2017/01/18)
Stereoselective total syntheses of (?)-histrionicotoxin and (?)-histrionicotoxin 235A are described. The 1-azaspiro[5.5]undecane skeleton was constructed diastereoselectively by a radical translocation–cyclization reaction involving a chiral cyclic acetal; the use of tris(trimethylsilyl)silane was crucial for the high diastereoselectivity. The cyclization product was converted into (?)-histrionicotoxin 235A through a one-pot partial-reduction–allylation reaction of a derivative containing an unprotected lactam. Finally, two terminal alkenes were transformed into enynes with the 1,3-amino alcohol protected as an oxathiazolidine oxide to complete the total synthesis of (?)-histrionicotoxin.
Total synthesis of (-)-histrionicotoxin
Adachi, Yohei,Kamei, Noriyuki,Yokoshima, Satoshi,Fukuyama, Tohru
, p. 4446 - 4449 (2011/10/05)
A total synthesis of (-)-histrionicotoxin was achieved. Our synthesis features preparation of a pseudosymmetrical dienyne through chirality transfer from an allenylsilane, a dienyne metathesis to produce the bicyclo [5.4.0] system in optically active form, selective functionalization of a diene via a 5-exo-trig iodoetherification, and an asymmetric propargylation.
Nitrone dipolar cycloaddition routes to piperidines and indolizidines. Part 9. Formal synthesis of (-)-pinidine and total synthesis of (-)-histrionicotoxin, (+)-histrionicotoxin and (-)-histrionicotoxin 235A
Davison, Edwin C.,Fox, Martin E.,Holmes, Andrew B.,Roughley, Stephen D.,Smith, Catherine J.,Williams, Geoffrey M.,Davies, John E.,Raithby, Paul R.,Adams, Joseph P.,Forbes, Ian T.,Press, Neil J.,Thompson, Mervyn J.
, p. 1494 - 1514 (2007/10/03)
An intramolecular hydroxylamine-alkyne cyclisation is used for the enantioselective synthesis of the cyclic nitrones 36 and 44. We have demonstrated the use of a novel nitrone protection strategy by cycloaddition of styrene to the cyclic nitrone 44 in the synthesis of the spirocyclic core of the histrionicotoxin family of alkaloids. Deprotection by dipolar cycloreversion of the styrene adduct (the bicyclic isoxazolidine 39) and in situ intramolecular dipolar cycloaddition of a pendant (Z)-α,β-unsaturated nitrile to the intermediate nitrone 50 gave the isoxazolidine 51 in high yield with a surprising degree of regioselectivity compared with the corresponding (Z)-enyne 36. The method is amenable to the synthesis of both enantiomers 51 and 62 of the tricyclic core structure which can be converted by way of the common intermediates (e.g. 53 and ent-53) respectively into the natural configuration of alkaloids (-)-histrionicotoxin 1 and (-)-histrionicotoxin 235A 65 as well as the unnatural (+)-histrionicotoxin 63.
A TOTAL SYNTHESIS OF d,l-HISTRIONICOTOXIN
Carey, S. C.,Aratani, M.,Kishi, Y.
, p. 5887 - 5890 (2007/10/02)
The first total synthesis of d,l-histrionicotoxin (1) from the spirolactam (5) is reported.
