6 橋状アジリジンの合成とIbogamine及びEpiibogamineの全合成
スポンサーリンク
概要
- 論文の詳細を見る
The total synthesis of ibogamine (1b) epiibogamine (1d) and desethylibogamine (1c) was accomplished by applying a new synthetic method for bridged aziridines as well as isoquinuclidines. This new method consists of the oxidation of δ,ε-unsaturated primary amines such as 4 with lead tetraacetate giving the highly strained bridged aziridines 5 which upon treatment with an acylating agent were cleaved mainly to isoquinuclidine derivatives 8. 1-Azatricyclo[3,2,1,0^<2,7>octane 5a obtained by this new method was cleaved readily with indole acetic anhydride in acetone to give the amorphous 13 which upon hydrolysis with aqueous potassium carbonate in methanol afforded the hydroxy derivative 14. The oppenauer oxidation followed by cyclization with 1,2-equiv. p-toluenesulfonic acid in benzene yielded the tosylate 16 which was then treated with sodium methoxide in boiling methanol to give the methoxy lactam 17. This compound on treatment with lithium aluminum hydride unexpectedly gave the enamine 18 which was hydrogenated on palladium to give the methoxy base 19. Finally, reductive elimination of the 18-methoxy group was accomplished smoothly with lithium aluminum hydride yielding desethylibogamine. Likewise, 21 and 22 were transformed to ibogamine (1b) and epiibogamine (1d) respectively.
- 天然有機化合物討論会の論文
- 1967-09-25
著者
-
永田 亘
シオノギ研
-
永田 亘
Shionogi Research Laboratories Shionogi & Co. Ltd.
-
奥村 保
シオノギ研
-
平井 章一
Shionogi Research Laboratories Shionogi & Co. Ltd.
-
平井 章一
シオノギ研
-
河田 享三
シオノギ研
関連論文
- Synthesis of 17-Hydroxyimino Steroids and their O-Alkyl Derivatives
- Uber angular substituierte polycyclische Verbindungen. III. Alkalische Degradation von 3α-Alkoxy-3β-amino-5β-cholestan-5-carbonsaure-γ-laktam.
- Totalsynthetische Untersuchungen an Steroiden. V. Reduktion von rac-17-Methoxy-D-homo-18-nor-androsta-4,8,13,15,17-pentaen-3-on mit Lithium in flussigem Ammoniak.
- Totalsynthetische Untersuchungen an Steroiden. IV. Synthese der Hydrophenanthren-sowie Hydrochrysenderivate.
- 6. dl-ジベレリンA_の生理活性
- Studies of Antitumor-Active 5-Fluorouracil Derivatives. I. Synthesis of N-Phthalidyl 5-Fluorouracil Derivatives
- Synthesis of Bridged Steroids. VI. B-Norsteroids having a Gibbane B-C-D Ring System. (1). Synthesis of 5-Cyano-B-norsteroids via Hydrocyanation
- Synthesis of Bridged Steroids. III. Cholestane Derivatives having a Bridged Bicyclo [2. 2. 2] octane Ring System of the Atisine Type
- Synthesis of Bridged Steroids. II. Steroids having a Bridged Bicyclo [3. 2. 1] octane Ring System of the Kaurene Type
- Synthesis of Bridged Steroids. I. Steroids having a Bridged Bicyclo [3. 2. 1] octane Ring System of the Phyllocladene Type
- Nuclear Magnetic Resonance Spectroscopic Evidence for Distorted Conformations of the C-Rings in 8β, 11β- and 11β, 13β-Bridged Steroids
- 28.新hydrocyanation法とそのステロイド合成への応用
- Angular Substituted Polycyclic Compounds. VII. Cyanation of ⊿^-2-Octalone (4,4a, 5,6,7,8-hexahydro-2 (3H)-naphthalenone).
- Total Synthesis of dl-3α-Acetoxy-5β-pregna-9 (11), 16-dien-20-one
- Totalsynthetische Untersuchungen an Steroiden. III. Uber das Verhalten von den C_-Carboniumionen der 2-oxygenierten 6-Methoxy-1,2,3,4-tetrahydronaphthalin.
- Totalsynthetische Untersuchungen an Steroiden. II. Synthese des 6-Methoxy-3,4-dihydro-2 (1H)-naphthalinons.
- 17 ペニシリン-α(R)-スルフォキシドの選択的合成 : ペニシリンからセファロチンへの変換
- Angular Substituted Polycyclic Compounds. II. Reaction of Cholest-4-en-3-one with Metallic Cyano Complexes.
- Synthesis of Bridged Steroids. IV. Cholestane Derivatives with a 3,5-Iminomethano Bridge
- 6 橋状アジリジンの合成とIbogamine及びEpiibogamineの全合成
- Synthesis of Bridged Steroids. V. Cholestane Derivatives having a Bridged 3-Azabicyclo [3. 3. 1] nonane Ring System
- Synthetic Studies on Isoquinoline Alkaloids. II. Selective Conversion of 3,9,10-Substituted Tetrahydroprotoberberines into 3,9,10-Substituted 14-Deoxoprotopines. Total Synthesis of 3,9,10-Substituted 5,6,7,8,13,14-Hexahydrodibenz (c, g) azecines
- Angular Substituted Polycyclic Compounds. VIII. Synthesis of trans-9-Methyl-2-decalone and trans-9-Aminomethyl-2-decalone from trans-2-Oxo-9-decalincarbonitrile.
- Totalsynthese von 3-Hydroxy-19-norpregna-1,3,5 (10)-trien-20-on und dessen 18-Oxo-derivat
- Studies on Seven-membered Ring Derivatives. III. : Partial Synthesis of 1,4-Dimethyl-7-ethylazulene (Lindazulene).
- Components of the Root of Lindera strychinifolia Vill. V. : Azulenes isolated from Linderene by Zinc-Dust Distillation.
- 第二種ベックマン転位に関する二・三の考察