天然有機化合物討論会講演要旨集

45 Prostaglandin合成中間体の立体選択的合成

高野誠一, 久保寺登, 谷川啓造, 小笠原国郎

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発行日: 1976/09/20
公開日: 2017/08/18

DOIhttps://doi.org/10.24496/tennenyuki.20.0_344

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1) Tricyclic tetrahydrofuran derivative(4) which was prepared from norbornadiene(3) was shown to be an excellent synthon for the preparation of the Corey aldehyde(16). (4) was cleaved reductively to the bicyclic ketene dichloride(5) with zinc and acetic acid which on tosylation, followed by the solvolysis afforded the epimeric tricyclic acetate(7). Hydrolysis, followed by the Jones oxidation of (7) yielded the tricyclic ketone(11) in excellent yield. Cyclopropane ring of (11) was cleaved with hydrobromic acid to give the bromo-ketone(12) which upon the Baeyer-Villiger oxidation, followed by heating with ethanol afforded the monocyclic ester(14). (14) was treated with silver perchlorate to give the lactone(15: R=H) which was converted to the Corey aldehyde(16) in excellent yield via the 4-phenylbenzoate(15: R=4-Ph-PhC-). 2) Optical active prostaglandin synthon(18) was prepared from the non-chiral diacetate(19) using micro-organisms. (19) was agitated aerobically with Bacillus subtilis var. Niger to give the chiral mono-acetate(20) which on heating with ethyl orthoacetate to give the ester(22). Hydrolysis, followed by acid cyclization of (22) afforded the optically active lactone (18).

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46 Prostagrandin誘導体の合成 : 12,15-ethanoprostaglandinsの合成

浜中信行, 黒野昌庸

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発行日: 1976/09/20
公開日: 2017/08/18

DOIhttps://doi.org/10.24496/tennenyuki.20.0_351

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12,15-Ethanoprostaglandins were synthesized in order to find out new drags which have a selected pharmacological activity isolated from many other inherent activities of prostaglandins. Our synthetic scheme is based on introduction of α-chain followed by ω-chain to the intermediate hemiacetal 30 derived from spiro[4,5]deca-1,4,8-trione 4. Reaction of sodium salt of cyclopentadione 1 and divinylketone 2 in DMF afforded a intermediate anion 3 which was treated with AcOH to give trione 4. The trione 4 was protected with ethylene glycol, oxidized with SeO_2 and further treated with LiCH_2CO_2^tBu to give hydroxy ester 24. Removal of the hydroxyl group from 24 was accomplished by chlorination with SOCl_2-pyridine followed by Zn-MeOH reduction. The resulting β,γ-unsaturated ketone 28 was isomerized to unsaturated ketone with NaOMe. The lactone 29 obtained from 28 by p-TsOH treatment was reduced to the key intermediate hemiacetal 30 with DIBAL. Introduction of α-chain to 30 by the conventional methods to furnish 31, which was deacetalized and treated with n-AmMgBr to give desired 12,15-ethano-13,14-dihdroprostaglandin F_<2α> methyl ester 33. Selective oxidation of 33 gave the corresponding prostaglandin E type compound 37.

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47 ビシクロ〔3.1.0〕ヘキサン誘導体を利用したシクロペンタノイド合成

常本大英, 梅本照雄, 高畑百合子, 近藤聖

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発行日: 1976/09/20
公開日: 2017/08/18

DOIhttps://doi.org/10.24496/tennenyuki.20.0_357

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Intramolecular addition of carbenoids derived from 2-diazo-3-oxo-6-alkenoates afforded 2-oxo-bicyclo[3.1.0]hexane-1-carboxylate derivatives. As the bicyclo compound contained activated cyclopropane moiety, mercaptide and cyanide anions were regiospecifically introduced to the 6-position to produce 2,3-disubstituted cyclopentanones. The cyclopentanone was proved to be a versatile intermediate for the synthesis of cyclopentanone derivatives, such as 11-deoxy PGF_<2α>, 11-deoxy PGE_1 and methyl jasmonate.

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48 Pederinの合成研究

続木一夫, 柳屋光俊, 渡辺隆啓, 中島康之, 松本毅

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発行日: 1976/09/20
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DOIhttps://doi.org/10.24496/tennenyuki.20.0_364

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Pederin, a potent insect poison isolated from Paedrus fuscipes, has been shown to have an unique polyether structure 1. We report here some of the results of studies on he synthesis of pederin. 1) Synthesis of d,1-pederamide 2 d,1-Pederamide 2 was synthesized in a stereoselective manner, starting from trans-butylene oxide, in 13 steps and in 1.8% overall yiels, through the sequence 6→7→10→13→2. The final product was identical (nmr, ir, tlc, ms) with pederamide obtained by degradation of the natural toxin. 2) Preliminary experiments toward the synthesis of pedaldehyd 1b Compound 24, which possesses essential structural features of pedaldehyde, was synthesized as a stereoisomeric mixture though the process outlined by 19→20→21→22→23→24.

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49 チャバネゴキブリ雄の翅上げ行動に関与する雌の性フェロモン

西田律夫, 桑原保正, 深海浩, 石井象二郎

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発行日: 1976/09/20
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DOIhttps://doi.org/10.24496/tennenyuki.20.0_372

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From the cuticular wax of the female German cockroach, Blattella germanica (L.), two components of sex pheromone responsible for male wing-raising were isolated as crystalline forms, and characterized as 3,11-dimethyl-2-nonacosanone (Compound A, Ia) and 29-hydroxy-3,11-dimethyl-2-nonacosanone (Compound B, Ib). Compound A and B independently elicits the wing-raising behavior, and Compound B is almost 10 times more active than Compound A. Both of synthetic compounds also exhibited the identical biological activity to those of natural ones, respectively. Besides Compound A and B, a minor component of the pheromone Compound C) was detected, and was identified as 29-oxo-3,11-dimethyl-2-nonacosanone (Ic). Of two asymmetric carbon atoms in Compound A, carbon-3 was concluded to be S-configuration. Several analogues of the pheromone were synthesized in order to figure out the effect of structural modification of the pheromone on the biological activity.

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50 サンショウ属植物成分の研究 : Benzo〔c〕phenanthridine型アルカロイドの化学とIwamideの構造

石川勉, 石井永

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発行日: 1976/09/20
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DOIhttps://doi.org/10.24496/tennenyuki.20.0_380

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Decarine (6), a monophenolic benzo[c]phenanthridine alkaloid, and iwamide (11), a modified amide from benzo[c]phenanthridine alkaloid, were isolated from the bark of Xanthoxylum arnottianum Maxim. In order to establish the location of the methoxy group of decarine (6), we measured the sift of the NMR spectra of several oxybenzo[c]phenanthridine alkaloids having an N-Et group instead of an N-CH_3 group by addition of shift reagent and observed a large shift of the signal due to a methoxy group to lower field in the case of chelerythrine series but due to an N-substituent in the case of nitidine series. The fact that the signal due to a methoxy group fairly shifted to lower field in the NMR spectra of N-methyl and N-ethyldecarine derivatives indicates that the methoxy group of decarine (6) situates at C_7 position of benzo[c]phenanthridine nucleus. On the other hand, we chemically converted decarine (6) into iwamide (11) via Baeyer-Villiger like oxidation of an immonium group which was developed in the case of structual establishments of arnottianamide (7) and isoarnottianamide (8).

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51 セネシオ族植物のピロリチジンアルカロイドfukinotoxin,syneilesineおよび関連化合物の化学構造

引地学, 古谷力, 飯高洋一

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発行日: 1976/09/20
公開日: 2017/08/18

DOIhttps://doi.org/10.24496/tennenyuki.20.0_388

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Macrocyclic secopyrrolizidine, senkirkine(1) was isolated from Farfugium japonicum. The new cytotoxic alkaloids, syneilesine and acetylsyneilesine were isolated from Syneilesis palmata and determined as formulae 2 and 3 by chemical and spectral evidences. The new carcinogenic alkaloid, fukinotoxin isolated from young scape of Petasites japonicus was determined as formula 5 by chemical evidence and X-ray crystallographic analysis.

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52 Chaetomium globosumの代謝する細胞毒性物貭Chaetoglobosin A-Fの構造

関田節子, 義平邦利, 名取信策, 桑野晴光, 梅田誠

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発行日: 1976/09/20
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DOIhttps://doi.org/10.24496/tennenyuki.20.0_396

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In the course of mycotoxin screening, the strains of Chaetomium globosum were moticed by their characteristic cytotoxicity to cultured HeLa cells, inhibiting cytoplasmic cleavage to form multinucleated cells. The causative agents named chaetoglobosins A-F were isolated from the mold and their physical properties are shown in Table I and II. The precise PMR examinations revealed the partial formulae shown in Chart 1 for chaetoglobosin A and, along with other evidences such as the formation of B and D from A by acid-treatment (Chart 3), the structures (1), (2), and (3) (without stereochemistry) were proposed for chaetoglobosins A, B, and D. The stereochemistry including the absolute configuration of chaetoglobosin A was then established by the X-ray analysis as (1). Thus the structures of B and D were shown by the formulae (2) and (3). Since chaetoglobosin A isomerizes into C by base-treatment and such reactions were observed for B and D to form iso-B and iso-D, the structure (4) was proposed for C by the comparison of PMR data. The strcuture was later verified by the X-ray analysis by Springer, et al. The structures of F (5) and E (6) were again suggested by PMR data and then confirmed by the reactions shown in Chart 3. Cytotoxic effects of chaetoglobosins, in which the phenyl group in cytochalasins so far reported is replaced by an indol-3-yl group, are shown in Table III.

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53 Berberine及びその誘導体の光酸素化反応と関連アルカロイドへの変換

花岡美代次, 向智里, 濱中伊都子, 荒田義雄

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発行日: 1976/09/20
公開日: 2017/08/18

DOIhttps://doi.org/10.24496/tennenyuki.20.0_404

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Sensitized photo-oxygenation of tetrahydroberberine(1) in methanol afforded berberal(2), oxynorhydrastinine(3), pseudopianic acid methyl acetal(4), and the ketone(5), which were also obtained from dihydroberberine(8) in a shorter time by the same reaction. The reaction of berberine(9) gave selectively 5 and that of oxyberberine(10) afforded the keto-lactam(11) along with 3. The one-step biomimetic transformation of tetrahydroberberine methiodide(12) into allocryptopine(13) was accomplished by photo-oxygenation. This reaction will provide a general synthetic method for the protopine alkaloids.

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54 分子内不斉環化反応を用いるピロリジン,ピペリジン誘導体の合成

若林利生, 加藤喜規, 渡辺兼三, 斉藤政彦

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発行日: 1976/09/20
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DOIhttps://doi.org/10.24496/tennenyuki.20.0_410

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Novel asymmetric intramolecular Michael addition by chirall amide anions to α,β-unsaturated esters were performed for the asymmetric syntheses of (S)-2-oxo-5-pyrrolidine acetic acid 7 and 2-oxo-6-piperidine acetic acid 14. These acids were respectively related to (S)-(-)ecgoninic acid and (S)-(-)-sedamine in order to determine their absolute configurations. The unnatural amino acids [24, 25, 26] obtained by NaBH_4 reduction of the corresponding lactams were utilized for the asymmetric synthesis of the key steroid C/D intermediate 22. The mechanism of this asymmetric aldol condensation is also discussed.

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55 THE TOTAL SYNTHESIS OF COCCINELLINE AND PRECOCCINELLINE

William A. Ayer, Kimiaki Furuichi

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発行日: 1976/09/20
公開日: 2017/08/18

DOIhttps://doi.org/10.24496/tennenyuki.20.0_417

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Precoccinelline and the corresponding N-oxide coccinelline are defensive substances secreted by certain members of the family Coccinellidae (polka-dot beetles or ladybugs). The synthesis of these alkaloids is described. The starting material is 2,6-lutidine which was first alkylated on the 2-methyl group with (β-bromopropionaldehyde acetal then acetylated on the 6-methyl group. Reduction of the protected ketoaldehyde with sodium-isoamyl alcohol gave predominantly the cis-2,6-piperidine derivative which afforded a mixture of two tricyclic ketones when cyclized using pyrrolidine and acetic acid. The appropriate tricyclic ketone was transformed in three steps to precoccinelline. Oxidation of precoccinilline gave coccinelline. The unusual isomerization of the cis-2,6-piperidine derivative during the cyclization step is discussed.

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56 dl-Pumiliotoxin Cの立体選択的合成

森裕二, 佐治幾太郎, 田中圭, 真崎規夫, 井深俊郎, 犬伏康夫

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発行日: 1976/09/20
公開日: 2017/08/18

DOIhttps://doi.org/10.24496/tennenyuki.20.0_422

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Racemate of pumiliotoxin C (1) which is a toxic constituent of Neotropical frogs, Dendrobates pumilio and D. auratus, was synthesized by stereoselective methods. The starting materials chosen for the present synthesis of the base (1) are cis-tetrahydroindanone (12), and new 1,3-bis(tri-methylsiloxy)-1,3-dienes (8) and (9). The Beckmann rearrangement of the oxime (13) afforded the quinolone (14), which was derived into the N-benzyl compound (15). Successive treatments of (15) with MCPBA, 48% aq. HBr, CrO_3-H_2SO_4, and Li_2CO_3-LiBr gave the enone (19). Stereoselective conjugate addition of LiCuMe_2 to (19) yielded the N-benzyl keto-lactam (11). The Diels-Alder reaction of cyclic diene (8) with acrylonitrile, followed by 10% aq. HCl treatment gave the keto-nitrile (26). Successive treatments of (26) with C_5H_5NHBr_3, NaBH_4, Zn-AcOH, and 15% HClO_4-AcOH gave the keto-lactam (10) as a sole product. Another synthetic route to the keto-lactam (10) was as follows. Reaction of the acyclic diene (9) with ethyl crotonate yielded the adduct (32), which was derived into the ketal-ester(33). Treatment of (33) successively with LiAlH_4, n-BuLi-TsCl, CuCH_2CN, aq. H_2O_2-NaOH, dil. HCl, and NaOMe-MeOH afforded the keto-lactam (10). The keto-lactam (10) and N-benzyl keto-lactam (11) were derived into the lactam (7). Reaction of (7) with P_2S_5 gave the thiolactam (41), and subsequent treatment of (41) with bromoacetone afforded the thiazole (42), which was derived into dl-pumiliotoxin C in five steps. Alternatively, heating of N-butyryl compound (48), which was prepared from (7), with CaO afforded the imine (49). Catalytic hydrogenation of (49) gave dl-pumiliotoxin C as a single product.

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57 エナミドを用いたClavine類の合成研究

二宮一弥, 木口敏子, 内藤猛章

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発行日: 1976/09/20
公開日: 2017/08/18

DOIhttps://doi.org/10.24496/tennenyuki.20.0_430

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The reaction of cyclohexanone with acrylamide was shown to afford quinolones in one step, which were also prepared from the reaction of cyclohexanoneimine with acryloyl chloride. In order to exploit the route for preparing the clavines (A), which have an indolo[4,3-f,g]quinoline skeleton, some extensions of the above reaction have been studied. As a result, benzo[f]quinolines (8, 10, and 22) were readily prepared either by thermal annelation of 2-tetralone with methacrylamide, or photocyclisation of the methacrylamides (7 and 9) of 2-naphthylamine and the methacrylamide (21) of 2-tetraloneimine. Indolo[4,3-f,g]quinolones (15, 16, 26, and 27) were also prepared either by photocyclisation of the methacrylamide (14) of 4-aminonaphthostyril, annelation of the 4-ketohexahydrobenz[c,d]-indole (23) or its imine (24) with methacrylamide, or more effectively, by acylation of the imine (24) with methacryloyl chloride. The latter reaction yielded a 1: 4 mixture of the uncyclised amide (25) and the cyclised lactam (26), of which (26b) was successfully converted into the 6,8-dimethylergolines (32, 33, and 34), which were identified as costaclavine (32), epicostaclavine (33), and festuclavine (34) respectively. The n.m.r. spectra of four stereoisomers of 6,8-dimethylergoline unambiguously established their stereochemistry.

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58 イソキノリンアルカロイドの合成研究

折登一彦, 伊藤光臣, S. O. deSilva, R. Rodrigo, R. H. Manske

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発行日: 1976/09/20
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DOIhttps://doi.org/10.24496/tennenyuki.20.0_438

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Conceptually new schemes of synthesis of isoquinoline alkaloids are introduced, in connection with studies of the electrophilic substitution reaction on phenethylamine derivatives. The spiroketone V, a key intermediate, was synthesized from N-acetyl 3,4-dimethoxyphenethylamine by several steps. Base treatment of V produced the indene VI, which possessed the 3-benzazepine moiety characteristic of the rhoeadine alkaloid, fused in the correct manner to a potential CD system with the desired substitution paterns. Base-catalyzed oxidation of VI (Triton B in pyridine-molecular oxygen) afforded the bright red indenone VII, which on Rose Bengal sensitized photooxygenation yielded the ketolactone VIII. Sodium borohydride reduction of VIII followed by dilute hydrochloric acid treatment produced the cis-lactone IX. Subsequent reduction with diisobutylaluminum hydride and methylation led to the total synthesis of (±) cis-alpinine XI. Interaction of XIIa,b, obtained by hydrolysis of Va,b, with bromine yielded the bromides whose treatment with tryethylamine afforded the spiroketones XIIIa,b, respectively. Similar conversions with VIIa,b led to XVa,b, by way of XIVa,b, respectively. XIIIb had previously been converted to the ochotensimine. Thus a new total synthesis of ochotensimine has been achieved. The scheme to provide XVa,b promises to lead to a very convenient route to the ochrobirine type of alkaloid. A study on synthesis of the phthalide isoquinoline alkaloid are now underway and also will be discussed.

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59 多環系インドールアルカロイドの合成研究 : 2,3のaspidosperma系アルカロイドの全合成並びに二量体型アルカロイド合成の試み

本間靖, 伴義雄

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発行日: 1976/09/20
公開日: 2017/08/18

DOIhttps://doi.org/10.24496/tennenyuki.20.0_444

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In the series of these studies on the syntheses of poly-cyclic indole alkaloids, the following aspidosperma alkaloids were synthesized from a common intermediate(1). (i) (±)-Fendleridine[=aspidoalbidine(6a)] (Aspidoalbine type) (ii) (±)-Aspidofractinine(14) (Refractine type) (iii) (±)-Deoxyaspidodispermine(20) (Aspidodispermine type) On the other hand, the modified Polonovski reaction of catharanthine(21) with vindoline was developed by Potier et. al., to give the dimeric indole derivative involving the natural configuration at C-18. Thus, for the synthesis of vinblastine or vincristine which are well known to be anticancer agents, an oxygen functional group should be introduced to the double bond of catharanthine in the correct form. In line with this principle, catharanthine was oxidized with Hg(OAc)_2 to give the lactam(22), whose acid was subjected to the iodolactonization, followed by reduction with (n-Bu)_3SnH. The compound (28) was further reduced with BH_3 to furnish the lactone(29), which was hydrolyzed to the corresponding hydroxy acid. However, this hydroxy acid was treated with diazomethane to immediately afford the initial lactone instead of the hydroxy ester. As the reaction condition have not thoroughly examined, the hydroxy ester(30) might be obtained under strict reaction condition. Thus, the dimerization of the lactone(29) with vindoline was attempted, the results of which will be discussed.

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Author Index

原稿種別: 索引
p. 452-455
発行日: 1976/09/20
公開日: 2017/08/18

DOIhttps://doi.org/10.24496/tennenyuki.20.0_452

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奥付

原稿種別: 付録等
p. App4-
発行日: 1976/09/20
公開日: 2017/08/18

DOIhttps://doi.org/10.24496/tennenyuki.20.0_App4

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