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畑中 顕和, 梶原 忠彦, 関谷 次郎
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Leaf alcohol, cis-3-hexenol, and leaf aldehyde, trans-2-hexenal, are widely distributed in fresh foliage, vegetables and fruits and are resposible for the characteristic leaf odor. In addition, they are both found in some insect excretions as functioning attractants and repellents. The investigation of leaf alcohol has been carried out by Takei and Ohno et al. since 1938. In this paper, cis-3-hexenal was confirmed in the macerated tea leaves, as being a precursor in the biosynthesis of leaf alcohol, and the process of biosynthesis was clarified linolenic acid and cis-3-hexenal were found in macerated leaves of Thea sinensis and this aldehyde may be produced from linolenic acid by an enzyme contained in macerated tea leaves in the presence of oxygen. This aldehyde was easily isomerized to trans-2-hexenal, and was converted to cis-3-hexenol by alcohol dehydrogenase. During maceration of freshly picked tea leaves, the amounts of trans-2-hexenal quickly increased and were influenced by maceration time, heating, oxygen and the pH. The synthetic activity of cis-3-hexenal was localized in chloroplasts of Thea sinensis leaves. 13-L-Hydroperoxy-linolenic acid also acted as a precursor, but not triglyceride and methylester of linolenic acid. This enzyme system appeared to be tightly bound to the lamellae membranes of chloroplasts. The alcohol dehydrogenase catalyzing cis-3-hexenal to leaf alcohol was purified from Thea sinensis seeds(variety: zairai). The substrate specificity of the ADH for hexenals, hexenols and terpenoids was discussed.
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井上 博之, 上田 伸一, 上里 新一, 小林 孝次
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The biosynthesis of iridoid glucosides that have a 11-methyl group such as lamioside (10b) and deutzioside (13b) has been investigated by administering (2-^<14>C)-mevalonic acid (MVA) and other labeled compounds to Lamium amplessicaule and Deutzia scabra, respectively. As a reference, (2-^<14>C)-MVA was also administered to Galium spurium var. echinospermon which contains asperuloside (14a) but no 11-methyl glucoside. Chemical degradation of (10b) and (13b) revealed nonrandomization of the labeling between C-3 and C-11 and retention of about half of the radioactivity at C-3 in both substances. Glucosides bearing a 11-carbomethoxy group such as lamiide (11a) and ipolamiide (12a) occurring with (10b) in the Lamium plant also showed the same labeling pattern. Radioactivity from tritium labeled (10-^3H)-7-deoxyloganic acid (5) and the corresponding 11-hydroxymethyl compound (20) was incorporated into lamioside (10b) suggesting the biosynthetic sequence CH_3 (on C-4)→CH_2OH→COOR. Results of the administration of (2-^<14>C)-MVA to G. spurium var. echinospermon followed by chemical degradation of the radioactive (14a) provided evidence for the formation of this glucoside via a pathway which does not involve randomization of the labeling of (2-^<14>C)-MVA. Experiments using several possible precursors such as (10-^3H)-10-hydroxygeraniol and a 11-methyl iridoid glucoside (19) are in progress.
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今井 邦雄, 片山 正人, 丸茂 晋吾
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We have previously shown that the metabolic transformation of isoprenoids by fungi gave interesting structural modifications on the substrates ; 1) Helminthosporium sativum converts racemic 10,11-epoxyfarnesol into its S(-)-glycol derivatives, and the other fungus, Colletotrichum nicotianae it into the corresponding R(+)-enantiomer, 2) the former fungus catalyzes a trans-cis isomerization of the Δ^<2,3>-double bond of farnesol (Fig. 1). We wish now to report our further advances made on these subjects summerized in the following four parts. 1) C. nicotianae metabolized racemic C_<16>-juvenile hormone (JH) into its R(+)-dihydroxy-derivative, whose enantiomeric composition was determined as 95:5. From this diol metabolites, optically active C_<16>-JH was chemically prepared (Fig. 2). (-)-14,15-epoxygeranylgeraniol, a constituent of the Brazilian plant with a chemoprophylactic activity in shistosomiasis, was synthesized by coupling R(+)-methyl 6,7-dihydroxygeranioate, obtained in pure form as a metabolic product of methyl geranioate by C. nicotianae, with the carboxylic derivative, obtained as a metabolic product of linalool by H. sativum (Fig. 4 and 5), establishing thus the natural product to have the S configuration. 2) Optically pure natural and unnatural C_<16>-JH were prepared in hopes of establishing structure-activity relationship from diastereomers 13 and 12, respectively, which were obtained as a result of complete optical resolution of racemic ethyl 10,11-dihydroxyfarnesoate as its C_<10>-etienyl ester (Fig. 6). 3) 10,11-Epoxysqualene was first found naturally in the mycelial mat of the fungus, Sclerotinia fructicola (Fig. 7). 4) Stereochemistry of the C_1-hydrogen exchange during dehydrogenation-hydrogenation reaction which plays an important role in the trans-cis isomerization of farnesol by H. sativum, was investigated using deuterium-labelled substrates, concluding that the pro R- and not pro S-hydrogen is replaced stereospecifically in this reaction (Fig. 11).
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冨田 裕, 妹尾 修次郎, 桜井 栄一, 通 和夫
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We report the biosynthesis of oleanene- and ursene-type triterpenes, oleanolic acid (7), maslinic acid (8), 3-epimaslinic acid (9), ursolic acid (10) and 2α-hydroxymaslinic acid isolated from the Isodon japonicus tissue cultures. 3-Epimaslinic acid was biosynthesised from (8) via 3-oxo derivatives, and then the mechanism involving cyclization of (3R)-2,3-oxidosqalene can be excluded in the biosynthesis of 3α-hydroxytriterpene. The ^<13>C-labelling patterns elucidated by ^<13>C NMR spectroscopy in these triterpenes synthesised from (4-^<13>C)mevalonic acid and (1,2-^<13>C_2)AcONa. The results are entirely in accord with Ruzicka's hypothesis for cyclisation of squalene to β-amyrin (37→38→39→40→41). Furthemiore the biosynthesis of ursene-type triterpenes proceed along a route (37→38→39→40→42), and an alternative mechanism involving an intermediate (43) for α-amyrin can be excluded.
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森 謙治
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(S)-(-)-Frontalin (4') was synthesized and shown to be attractive to western pine beetles, while (R)-(+)-enantiomer (4) was inactive. This proved the chiral nature of the pheromone receptor of the insect. Two pheromones, sulcatol (8) and ipsenol (14), were synthesized from amino acids in optically active forms. Since these pheromones are derivatives of monoterpenes, amino acids can be regarded as usedful starting materials for the synthesis of chiral terpenes. Natural (-)-ipsenol (14) was shown to possess S-configration by its derivation from (S)-(+)-leucine (16). A noteworthy feature of the ipsenol synthesis was the use of an optically active α-methylene-γ-lactine (22) as the key intermediate.
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藤沢 有, 太田 博道, 小堀 武夫, 畑 和水, 酒井 邦和
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Several five-membered carbocyclic compounds having two alkyl chains at the vicinal positions are known as biologically active natural products. Although the most simple and reactive five membered cyclic compound is cyclopentadiene, there is no report on the general method for the introduction of two kinds of carbon chains into the vicinal positions of the diene. A method for the selective preparation of cyclopentadienes with two kinds of carbon chains at the vicinal positions was investigated by treating esters of cyclopentadienylethanols, prepared from sodium cyclopentadienide and epoxides, with a base. The present method was successfully applied to the synthesis of C_9-terpene lactones, i. e. oniku- and mitsugashiwa-lactones (16 & 17) isolated as the physiologically active principles of Boshniakia rossica Hult and Menyanthes trifoliata L, from the intermediate anion (10) of cyclopentadienolactone prepared from cyclopenta-dienylethyl methyl carbonate (7a). Arethrolone (26a) was prepared from 2-methylcyclopentadienylethanol (18) obtained by the reduction of 10. The method is expected to be generally applicable to the syntheses of the natural products with vicinally dialkylated five-membered carbocyclic structure. As an example, routes to two prostanoids will be also discussed.
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Gilbert Stork, 磯部 稔
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New general routes to prostaglandins involve 3-substituted 4-hydroxy-2-methylene cyclopentanones 1. These are prepared by regiospecific formation of the proper cyclopentanone enolate (derived from either cracking of the diphenyl enolphosphinate or conjugate addition of 4-cumyloxy-2-cyclopentenone) followed by formaldehyde trapping and subsequent conjugate addition of the acid side chain precursor. The total syntheses of (±) and (+)PGF_<2α> is described.
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廣田 洋, 棚橋 善昭, 高橋 武美
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Structure elucidation of LB, one of the volatile components of "San-shion" (Ligularia species), was accomplished in the following way. LB, C_<15>H_<26>O, was assumed to be a saturated guaiane-type sesquiterpene ether from its spectra and the dehydrogenation reaction. INDOR experiments on LB and 1-epiguaioxide(13) showed that LB is one of the eight stereoisomers of guaioxide(10). As six compounds of them are already known, the structure of LB must be represented by either 14 or 16. The reaction of LB with NBS in CCl_4 gave 4-bromo-LB(22) in 8〜18% yield. The compound(22) was dehydrobrominated into 23, which reacted with diborane to give 27. The oxidation of 27 with Jones' reagent gave the ketone(29), which then isomerized to 26. The structure of 22, 23, 26, 27, and 29 were confirmed by their spectral data, obtained by double resonance and lanthanide-induced shift techniques in PMR. The absolute structure of 29 was determined by the ORD and CD experiments. The hydrogenation of 23 gave 4-epi-LB. The compound(14) obtained by tosylation of 27 followed by reduction with LiAlH_4, was identical with 4-epi-LB. Therefore, the structure of LB was determined to be 16, including the absolute configuration.
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稲山 誠一, 川又 健, 大倉 多美子, 飯高 洋一, 坂井 昭子
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A novel pseudotwistane named pulchellon (1) was first isolated from a collection of Gaillardia pulchella as a minor constituent along with the pseudoguaianolide alkaloids, pulchellidine and neopulchellidine. The absolute stereostructure of pulchellon (1) has been completely established as designated in Fig. 1 on the basis of its chemical and spectral evidences together with the biogenetic consideration as well as the direct three dimentional X-ray cryst-allographic analysis of pulchellin itself. A synthetic approach to pulchellin (1) from another constituent pulchellin (2a) has been studied through a possible biogenetic pathway proposed earlier.
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浅川 義範, J.-C. MULLER, G. OURISSON, J. FOUSSEREAu
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Some occupational allergies (contact dematitis) associated with the handling of European woods are caused by epiphytic Bryophytes, namely Hepaticae such as Frullania. We have previously described the isolation and the synthesis of (-)-frullanolide (1), a new sesquiterpene lactone possessing allergenic properties from Frullania tamarisci. Patients sensitive to crude extracts of Frullania are usually highly sensitive to pure frullanolide. However, there are a few exception, which led us to search for other components of Frullania extracts, and we describe now the isolation of seven further new lactones of eudesmane and eremophilane series (Ent-1, Ent-9, Ent-15, 11, 12, 13 and 14) possessing the unusual 7-α configuration from Frullania dilatata and β-cyclo-costunolide (17), a new 4-β-OH(ax)eudesmanolide (19) and a new sesquiterpene aldehyde (21) possessing the 7-β configuration from F. tamarisci subsp. obscura. Twelve patients sensitive to Frullania were tested to the new lactones isolated from F. dilatata. All our patients sensitive to Frullania are sensitive to at least one of the α-methylene-T-butyro lactone. It is noteworthy that (1) in F. tamarisci and (Ent-1) in F. dilatata are the major components, however 4-β-OH eudesmanolide (19) is the major one in F. tamarisci subsp. obscura and cis-lactones have not been detected from this species. The biogenesis of the present sesquiterpene lactones may be rationalized by assuming the strightworword acid-catalized cyclization of costunolide type (18) and of inunolide type (23) precursor.
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林 雄二, 西沢 麦夫, 植村 元一, 目 武雄
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Illudoid and seco-illudoid constituents have been isolated from a fern, Hypolepis punctata (Japanese name: Iwahimewarabi). 1). Pterosins, H (1), Z (3) and I (4), were alkyl indanone derivatives with illudane skeleton. The structures were determined by spectral analyses, interconversions and total synthesis. 2). Other natural pterosins, ( )-pterosin D (16) and onitin (18), were derived from pterosin Z (3). 3). Hypacrone (19), a novel seco-illudoid, was a characteristic acrid principle of the fern. The structure was deduced by spectral analyses and by transformation into pterosins on acid treatment. 4). A short-step total synthesis of hypacrone was accomplished. This includes a cross aldol condensation of two major fragments, a cyclopentenone (33) and a 1,3-diketone (23). Dehydration of the aldol product (35) gave 6,7-trans-hypacrone (36), which was equilibrated with 6,7-cis-isomer (natural hypacrone) by sensitized irradiation. Pure cis-hypacrone was isolated by careful chromatography of the cis-trans mixture on neutral alumina.
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野副 重男, 古川 淳, 磯村 八洲男, 三川 潮
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The crude metabolite obtained from the cultured micellium of Coriolus consor a mushroom which produces coriolin and the related compounds was found to contain a hydrocarbon, hirsutene which has been thought to be a biosynthetic intermediate of coriolin, hirsutic acid and complicatic acid etc. The hydrocarbon fraction was purified by preparative tic(silica gel/AgNO_3/benzene) to afford pure hirsutene4, C_<15>H_<24>(M^+, 204), which was converted to the norketone 6, C_<14>H_<22>O (M+, 206)(ir; 1740 cm^<-1>) by oxidative cleavage. In order to confirm the structure , and to prepare the labelled substrate for biosynthetic study, total synthesis of hirsutene was attempted. Cope rearrangement of the diene 9 obtained from the known ketone 8 afforded the diene 10 in quantitative yield. Oxidative shortening of the side chain followed by treatment with oxalyl chloride gave the acid chloride , which was cyclized to the tricyclic ketone 13 (SnCl_4/CS_2). Reductive removal of chlorin followed by Wittig methylenation yielded hirsutene which was shown to be identical with natural hydrocarbon. Preparation and feeding experiment of labelled hydrocarbon are under investigation.
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城戸 英郎, 藤下 利夫, 堤 憲太郎, 吉越 昭
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β-Vinylbutenolide (2), which was conveniently prepared from β-vinylbutyrolactone (12) in 45% overall yield, reacts with active methylene compounds as an acceptor in 1,6-Michael addition. Some active methylene compounds were examined. In the case of 2-methylcyclohexane-1,3-dione (1), its enolates yielded a mixture of epimeric annelation products, 19 and 20, the forever compound being the major product (Table 1). The stereochemistry of these products were elucidated. Some transformation of 19 and the structure of the transformation products have been discussed.
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小杉 紘史, 宇田 尚
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Syntheses of (±)-grandisol, (±)-canadensolide, and (±)-fomannosin have been investigated by the use of photocycloaddition reactions of α,β-unsaturated lactones with olefins as the key steps. i) (±)-Grandisol has been stereoselectively synthesized from the photoadduct (3) between β-methyl-Δ^<α,β>-δ-lactone (2) and ethylene-(Fig. 1) ii) Bislactone (14), the precursor of (±)-canadensolide has been obtained from the photoadducts of γ-n-butyl-γ-crotonolactone with 1,1-dimethoxy ethylene. However, attempts to introduce exomethylene group have failed. -(Fig. 2) iii) Synthesis of deoxy dihydro fomannosin has been achieved starting from the photoadduct (19) of β-(4,4-dimethyl-2-oxocyclo-pentyl)-Δ^<α,β>-butenolide to ethylene. -(Fig. 3.4.5.)
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北谷 克司, 桧山 為次郎, 野崎 一
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Reaction of dihalocyclopropane with large excess lithium di-alkylcuprate gives 1-alkyl-1-metallocyclopropane, which is stable enough to react with other electrophiles. The reaction has been stereochemically controlled and applied to dl-sirenin synthesis.
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伊沢 誠, 伊東 敏雄, 大船 泰史, 橋本 久信, 東 静男, 丸山 文夫, 柳屋 光俊, 白浜 晴久, 松本 毅
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Synthetic routes to coriolin 1 were studied. The key bicyclic intermediate 3 corresponding to the A/B rings of 1 was synthesized from dicyclopentadiene through several steps. The highly functionalized B/C moiety model 44 was obtained from 22. Possible intermediates 52, 53, 54 and 55 for the biosynthesis of coriolin were synthesized through 50.
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長瀬 博, 京谷 善徳, 毛利 哲也, 五島 俊介, 増田 秀樹, 加藤 金芳, 鈴木 正昭, 山田 静之, 平田 義正
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A one-step reaction constructing a cis-hydrindan derivative (5) properly substituted for the synthesis of coriamyrtin (1) from a cyclo-hexenone derivative (4) was carried out. Since the conversion (4)→(5) involves the intermediary formation of the tricyclic compound (6), this type of compound [i.e., (10)] was synthesized from the cyclohexenone (4). By the transformation of functional groups in (10) using a series of stereocontrolled reactions, the derivative (10) was converted to a cis-hydrindan (15) possessing desired functionality and stereochemistry. Further, the cis-hydrindan (15) was transformed into the γ-lactone (23) by the following sequence: (15)→(16)→(17)→(18)→(19)→(20)→(21)→(22)→(23).
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坂井 文秀, 大熊 広昭, 今西 英世, 越山 日出男, 内藤 隆之, 川口 洋
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Breynins A (C_<40>H_<56>O_<23>S) and B (C_<40>H_<56>O_<24>S), which have been isolated from Breynia officianlis Hemsl (Family Euphorbiaceae), are new sulfur-containing glycosides with potent hypocholesterolemic activity. Acid hydrolysis of breynin A (I) in methanolic hydrochloric acid afforded glucose, rhamnose, p-hydroxy-benzoic acid and the aglycone, breynogenin (II, C_<22>H_<26>O_9S), along with its secondary degradation products, breynolide (III, C_<15>H_<22>O_7S) and isobreynogenin (IV, C_<22>H_<26>O_9S). The structure of II was determined to be a p-hydroxy-benzoyl ester of III, the site of esterification being the C-11 axial hydroxyl group of III (Fig. 2). It is most probable that IV is a conformational isomer of II with the tetrahydropyranyl ring of II being inverted in IV, since IV has an axial methyl at C-12 and an equatrial ester group at C-11 (Fig. 3).
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一の瀬 功, 熊沢 智, 小林 東洋彦, 加藤 忠弘, 北原 喜男
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Directed toward the biogenetic type Synthesis of terpenoids from the polyene progenitors, the following two topics (I, II) are discussed. I. Selective C-C bond formation of Polyenes 1. Intermolecular acylation. Geraniol derivatives (4a) and farnesyl cyanide (11) are effectively acylated to give 5 (or 6) and 13 (and 14), respectively. The products 9 and 10 are expected to be the intermediate for taxin synthesis while 14 is converted to the synthetically useful intermediate (21). 2. Intramolecular acylation. For the constraction of carbon skeleton of terpenoids, 22 and 34 were treated with SnCl_4 to give 28〜30 and 35, respectively. 35 was transformed into ± mukulol (32). II. Brominative Cyclization of Polyenes 46 was found to be a new reagent for the brominative cyclization of polyenes. 48 and 49 were formed from 47 by the action of AlX_3. 46 is also effective for the terminal bromination of 47 and 50.
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相沢 宏保, 綱川 光明, 佐々木 伸樹, 加藤 忠弘, 北原 喜男
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Recently, we reported the structure of two new diterpenoids, named monilactone-A (M-A) and -B (M-B), which were isolated from the rice husk. Although partical structure around A ring of these terpenoids are quite similar to that of gibberellins (G-A) excepting the absolute configuration, momilactones exhibited the growth inhibition activity, while the later is the promotor of higher plants. It is of interest to find the active portion of momilactones toward the inhibition. For this purpose chemical transformation of momilactones was carried out to obtain the derivatives and the result was shown in fig 2. Of these the strongest activity were observed in acetyl M-B (XII), followed by monool (V) and M-B. Physical evidence of these derivatives are also discussed to establish the structure of momilactones chemically.
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福井 宏至, 山崎 幸苗, 根守 良一, 臼田 定和, 小清水 弘一
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Two new kaurenolides A and B, four new gibberellins C, D, E and F, and plant growth-inhibitory factors G, H, I, J, K, L, M, N and O have been isolated from seeds of pumpkin (Cucurbita pepo L.). Their structures have been elucidated on the basis of spectral data and chemical evidences. On the rice seedling assay, A, B, D (GA_<39>) and E were inactive, while F, an epimer at C-12 of E, was active. I and J completely inhibited the growth of rice seedlings at a concentration of 10^<-3>M. M, named cucurbic acid, and its derivatives N and O inhibited the growth of rice and lettuce seedlings at a concentration of 10^<-3>M, but showed no effect on Avena coleoptile assay. A possible biosynthetic pathway of cucurbic acid is discussed, and jasmonic acid could be biosynthesized from cucurbic acid by oxidation of the hydroxyl group at C-6 followed by epimerization at C-7.
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野出 学, 堀 均, 藤田 栄一
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We attempted the total syntheses of C_<20> gibberellins (GA_<15>, GA_<37>, and GA_<27>) from the key intermediate 2 used in the total synthesis of enmein (1), and the syntheses of GA_<15>(3) and GA_<37> methyl ester (36) were accomplished. The synthetic route is as follows. Hypoiodite reaction with compound 2 introduced the oxygen function into the C-19, and the resulting lactone was converted into a carboxylic acid (9) through the route shown in Chart 2. Subsequent introduction of an oxygen function to the C-7 was achieved by an epoxidation of enol lactone 12 derived from compound 9. The product 13 was converted into mesylate 18, which was subjected to rearrangement with alkali to give gibberellane derivative 19. The latter was transformed into compound 21 as shown in Chart 3. Gibberellin A_<15> methyl ester (26) was synthesized by the Wittig reaction from 17-nor-16-one 25 derived from 21 via four steps as shown in Chart 4. Since the hydrolysis of the methyl ester to GA_<15> has been reported, the present synthesis means the total synthesis of GA_<15>. Gibberellin A_<37> methyl ester (36) was yielded as the major product by the Meerwein-Ponndorf reduction of 3-one 35 which was derived from 31 (methyl ester of 21) via several steps of reactions as shown in Chart 5. The final hydrolysis of the ester 36 into GA_<37> itself (4) and the synthesis of GA_<27> are in progress.
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中田 忠, 斉藤 謹一, 渡邊 茂, 横田 勝弘, 田原 昭
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The synthesis of some natural products has been achieved from 1-abietic acid (1), a major component of pine rosin. I) Synthesis of A-Ring Substituted Natural Diterpene 1β-Bromo ester (15), a key intermediate in the synthesis of A-ring substituted diterpenes, was obtained by an interesting bromination (NBS, Ac_2O-c.H_2SO_4) of phenacylidene ester (14) derived from 1-abietic acid (1). Salviol (2), isolated from Salvia miltiorrhiza, and 2β-acetoxysugiyl methyl ether (3), isolated from Podocarpus ferrugineus, were synthesized from 1β-bromo ester (15) by several steps. II) Synthesis of Gibberellin A_<12> A/B-trans-Hydrofluorene compound (41), obtained via a benzilic acid rearaangement of dioxo ester (35) derived from 1-abietic acid (1), was converted by 8 steps into 13β-carboxy diester (84). Intramolecular carbene insertion of diazoketone (86) gave 5-membered ring ketone (87). After partial hydrolysis, half acid (88) was methylated to give diester (89), which was identical with GA_<12> nor-ketone dimethyl ester synthesized from natural GA_<12> (4). The conversion of half acid (88) into [^<14>C]gibberellin A_<12> had been accomplished by B.E. Cross, et al.
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今江 清人, 楠見 武徳, 柿沢 寛
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As the Synthetic approach to fernenes, a few attempts were made on the synthesis of trans-dimethylhydrophenanthrene (1), which corresponded to the B-C-D ring system of fernene. Acid-catalyzed cyclization of the phenethylcyclohexenone (3) proceeded stereoselectively to give the tricyclic compound (4). A cis-relationship of the two angular methyls of (4) was confirmed by an individual synthesis of authentic (11). The desired trans-compound (1) was obtained through a Claisen rearrangement of the vinyl ether (22), followed by several steps including a cyclization of (23). In this process, the required cyclohexenol (21a) was prepared effectively from the cyclohexenone (20) in three steps ; (20)-(21b)-(21a-benzoate)-(21a). These results were applied in the synthesis of (33). Moreover, the potent intermediate (41) was obtained through an amide-Claisen rearrangement of (35) which was converted to the lactone (37). The construction of the E ring system of fernenes using the diketone moiety of (41) is in progress.
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福山 愛保, 野老山 喬
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Studies directed to the total syntheses of several degraded limonoids will be presented in this lecture. Fraxinellone 1 has been synthesized by the condensation of 3-furyl lithium with 1-carbethoy-2-formyl-2,6-dimethyl-5-cyclohexene 11, which is prepared through Diels-Alder reaction between ethyl 3-methyl-2,4-pentadienoate and methacrolein and the following isomerisation of the double bond. In the synthesis of pyroangolensolide 6, the key intermediate 34 was produced from 4,8-dimethylhexahydro-3(9)-inden-2-one 21, which was prepared through Wichterle annelation of 2,6-dimethylcyclohexanone. The reaction of 34 with 3-furyl lithium affords pyroangolensolide 6 together with its diastereomer 36. The synthetic approach to calodendrolide 3 starts from 4,8-dimethylhexa-hydro-3(9)-inden-2-one 21, the same intermediate as in the synthesis of pyroangolensolide 6. The diepoxide intermediate 49, which posses 3,9-epoxide ring with the correct stereochemistry and the appropriate functionalities for further elaboration, has been derived.
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越智 清成, 永野 洋幸, 松永 功, 新藤 実, 金子 主税, 杉本 昭子, 山田 幸子, 石川 正幸, H. F. Deluca
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All of the so far reported syntheses. of 1α,25-dihydroxycholecalciferol which is "tissue-active" form of vitamin D_3 have used 1α,25-dihydroxycholesterol as a common key compound. We report here the synthesis of this active metabolite from cholesterol (I) without using 1α,25-dihydroxycholesterol as an intermediate. The procedure for the present synthesis can be devided into the following three parts: i) introduction of a hydroxyl group at C-25 of cholestanol, ii) dehydrogenation of 25-hydroxycholestanol (V) to 25-hydroxy-cholesta-1,4,6-trien-3-one (VII), and iii) preparation of 1α,25-dihydroxy-7-dehydrocholesterol (XII) from the hydroxytrienone (VII) and its subsequent conversion to 1α,25-dihydroxycholecalciferol (XIV). In the first part of the present synthesis, we have utilized the photo-induced 25-hydroxylation reaction of cholestanol acetate reported recently by Mazur et al. In the second part, 25-hydroxycholestanol (V) was dehydrogenated by DDQ to 25-hydroxycholesta-1,4-dien-3-one (VI), which was further dehydrogenated to 25-hydroxycholesta-1,4,6-trien-3-one (VII) by refluxing it in dioxane with chloranil in presence of dihydro-DDQ. In the third (final) part, the hydroxytrienone (VII) was converted to 1α,25-dihydroxy-7-dehydrocholesterol: provitamin D_3(XII) according to the procedure which was uncovered by us recently and utilized successfully in the syntheses of 1α-hydroxycholecalciferol and some of its related compounds. The application of the well known photochemical opening at the B-ring of this provitamin D_3(XII) and the thermal 1,7-antarafacial hydrogen shift of the resulted previtamin D_3(XIII) accomplished the synthesis of 1α,25-dihydroxycholecalciferol (XIV).
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石黒 正路, 梶川 明, 斉藤 博満, 赤岩 明, 森崎 益雄, 池川 信夫
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To obtain further information on the reactions and stereo-chemistry of steroids, synthesis of withanolides was investigated. As a model compound, the AB ring moiety of withaferin A (1), anti-tumor steroid, was synthesized from cholesterol. Dienone 7 was derived to 6α-hydroxy-dienone 18, which was converted to 31. The analogues, 19, 21, 22, 23, 36b, 37b and 40b, which have the similar functionalities in ring A/B as those of 1, have been synthesized through the key intermediate dienones 7 and 24. For the synthesis of side chain of 1-3, the coupling reaction of C-22-aldehyde with α,β-unsaturated esters was carried out. Reaction with α,β-unsaturated esters which have methyl groups at both α and β carbons gave γ-coupling product 46. This has the identical structure with 2 and 3 except for the stereochemistry at C-22 position. The stereochemistry of electrophilic reactions on C-22-ene 48 was investigated inorder to find a method of stereospecific introduction of 22R-hydroxy group.
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島田 和武, 藤井 洋一, 三石 悦子, 新崎 百合子, 南原 利夫
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Three new types of bufotoxins in which the succinoyl, adipoyl, and pimeloyl groups are displaced for the suberoyl residue of the so-called "bufotoxin" have been separated from the skin of Japanese toad Bufo vulgaris formosus Boulenger. In addition, four bufogenin 3-sulfates and two novel conjugated cardenolides named cardenobufotoxin have also been isolated. The ethanolic extract of the skin obtained from 1,800 toads was separated by chromatography on Amberlite XAD-2 resin, silica gel, and Sephadex LH-20 and, if necessary, by high-speed liquid chromatography to provide new cardiotonic steroid conjugates. The structures of these substances were elucidated to be resibufogenin 3-succinoylarginine ester (Id), bufalin 3-succinoylarginine ester (IIb), gamabufotalitoxin homologs (IIId, IIIh, IIIk, IIIm), bufogenin 3-sulfates (IV, V, VI, VII), and cardenobufotoxins (VIIId, VIIIf) by degradative and synthetic means.
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山内 辰郎, 阿部 フミ子, 高橋 道子
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Several yellow pigments were observed on TLC in the methanol percolate of root bark of N. odorum, and five of them, Y-9, -8, -7, -6 and -5 were isolated with the aid of silica gel column (Solv. CHCl_3-MeOH-H_2O and EtOAc-MeOH), polyamide column (Solv. H_2O) and preparative TLC. They are all glycosides, having same sugar moiety as odoroside K (uzarigenin β-gentiobiosyl-β-D-diginoside) (Y-7) or odoroside G (digitoxigenin β-gentiobiosyl-(1→4)-β-D-digitaloside) (Y-9 and Y-8), and Y-6 and Y-5 are de-monoglucosyl compounds of Y-9 and Y-8, respectively. The aglycone of Y-8, Y-7 and Y-5 (A-1) was determined as 3β-hydroxy-5β-carda-8,14,16,20: 22-tetraenolide and that of Y-9 and Y-6 (A-2) as a mixture of 21α- and 21β-hydroxyl derivatives of A-1. Since the configurations of the sugars to the both aglycones were found to be β, the structures of Y-9, -8 and -7 are represented as follows; Y-9: 3β-O-(β-gentiobiosyl-(1→4)-β-D-digitalosyl)-21-hydroxy-5β-carda-8,14,16,20: 22-tetraenolide; Y-8: 3β-O-(β-gentiobiosyl-(1→4)-β-D-digitalosyl)-5β-carda-8,14,16,20: 22-tetraenolide; Y-7: 3β-O-(β-gentiobiosyl-β-D-diginosyl)-5β-carda-8,14,16,20: 22-tetraenolide.
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野原 稔弘, 中野 章子, 宮原 一元, 古森 徹哉, 川崎 敏男
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A water-soluble glycoside, (mp 209-220°(decomp.)), [α]_D-116°, C_<47>H_<70>O_<24>, named trillenoside (I), was isolated from the rhizomes of Trillium kamtschaticum Pall. (Liliaceae). The structure of its aglycone (trillenogenin) (II), mp 250-251°, [α]_D-198°, C_<26>H_<36>O_8, was determined by X-ray analysis of the tetraacetyl monobrosyl derivative, mp 242-244°(decomp.), [α]_D-112°, C_<40>H_<47>SO_<14>Br, and I was characterized as 15-oxo-18-nor-25-D-spirost-5, 13-diene-1β, 3β, 21, 23α, 24β-pentaol 1-O-β-D-apio-D-furanosyl-(1→3)-α-L-rhamnopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-α-L-arabinopyranoside. I is a novel type steroid glycoside, 18-norspirostanol oligoglycoside, and other points to be noted in the structure are: 1) enone system in the D-ring; 2) hydroxyl group at C_<21>; 3) two hydroxyl groups in the F-ring; 4) apiose in the branched-chain tetrasaccharide moiety.
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北川 勲, 吉川 雅之, 池西 裕二, 任 光植, 吉岡 一郎
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In search of a new selective cleavage method of certain glycoside linkage in oligosaccharide-glycoside, three new methods for selective cleavage of a glucuronide linkage in saponin have been developed. I. Photolysis It has been found that ultraviolet irradiation is a convenient procedure for degradation of some oleanane-type saponins resulting in liberation of their genuine sapogenols (Table I). Studies on the structure requirement for the ready photolysis have shown that a glucuronic acid moiety directly connected to the sapogenol is an essential constituent in the carbohydrate portion (cf. glucuronide-saponin). II. Pb(OAc)_4 Degradation Pb(OAc)_4 oxidation followed by a brief treatment with alkali of permethylated derivative of glucuronide-saponin possessing free carboxyl function readily affords methylated sapogenol and methylated carbohydrate ingredients. For example, 23 is decomposed to 21 via 24 and 25 almost quantitatively, and 27 to 29, 30, 31, 32, and 33 via 28 in excellent yields. III. Ac_2O-Pyridine Degradation On heating in Ac_2O-pyridine (2:1) mixture, glucuronide-saponin possessing carbohydrate chains at C-2 and C-4 of its glucuronide moiety is decomposed to acetylated sapogenol and acetylated carbohydrate derivatives. To accomplish the degradation, both Ac_2O and pyridine are indispensable. The above described three methods seem to be useful in the structure study of polysaccharide containing the glucuronide linkage and the other kinds of uronide linkage.
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金子 光, 田中 美香子, 三橋 博
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Isolation of solanidine(1), etioline(3) and verazine(2) as main alkaloids from the terrestrial part of budding Veratrum grandiflorum (Max.) Loesen, has been reported. In addition to veratramine, two new alkaloids, teinemine((22R, 25S)-22, 26-epimino-cholesta-5-ene-3β, 16α-diol)(6) and isoteinemine((22S, 25S)-22, 26-epiminocholesta-5-ene-3β, 16α-diol)(7) were identified from the secondary alkaloid fraction in HCl hydrolysate of budding leaf glycoside. From the accumulation of three 22, 26-epiminocholestenes (etioline(3), verazine(2) and teinemine(6)) in the budding veratrum, they seemed to have an important role in the biosynthesis of solanidine(1). And the hypothetical pathway of solanidine(1) biosynthesis with these 22, 26-epiminocholestenes could be proposed. The next problem in our studies of solanidine(1) biosynthesis was to determine its nitrogen origin. In the cautious detection of annual change of alkaloids in veratrum plant, we found that verazine(2) already accumulated in the dormant rhizome, then we detected quantitative change of free amino acids and ammonia in whole plant during dormant period. Only L-arginine showed the significant change was appeared at just before the accumulation of verazine(2) in the rhizome. This result suggested that L-arginine was the possible nitrogen origin in solanidine(1) biosynthesis. And this suggestion was strongly supported by that the feeding experiment of ^<15>N-L-arginine with [4-^<14>C]-cholesterol showed the higher existence and incorporation of ^<15>N in solanidine(1) than ^<15>N-NH_4Cl feeding.
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及川 裕二, 黒沢 隆夫, 米光 宰
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セッションID: 33
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I. Synthesis of Olivacine and Ellipticine Acid-catalyzed cyclization of β-ketosulfoxides derived from indolepropionic acid derivatives afforded tetrhydrocarbazol-2-ones. This reaction was now applied for the synthesis of antitumor indole alkaloids, olivacine (1) and ellipticine (19). Methyl indolepropionate (5) was converted with Et_2SO to a keto-sulfoxide (8) (95%), which was cyclized to a tetrahydrocarbazolone (10) (51%). To the carbonyl group in 10 butyl acetate was added in the presence of BuLi to give an adduct (11) (97%), which was converted to a carbazole-2-acetic acid derivative (13) (98%). Olivacine (1) was easily synthesized from 13 through a series of usual methods. Overall yield of 1 from 5 was 28%. Similarly, ellipticine (19) was synthesized from methyl indolebutylate (20) in 23% overall yield. II. Synthesis of Estrone Although there are so many reports on the synthsis of estrone, more practical methods are still required because of invaluable physiological properties of estrogens. Thermal elimination of β-ketosulfoxide gives αβ-unsaturated ketone. This reaction was now applied for the synthesis of key intermediates (35,36) in the Smith's estrone synthesis. A β-ketosulfoxide (30) derived from ethyl m-methoxyphenylbutyrate (29) and Me_2SO was methylated with MeI to 31 (91%). Thermal elimination of 31 gave αβ-unsaturated ketone (33), which was condensed with methylcyclopentanedione (34) to give 35. More conveniently 31 was heated in the presence of 34 in diglyme to give 35 (70%) through the elimination and Michael addition. 32 prepared from 29 and EtS(O)C_6H_5 gave directly an acid-catalyzed cyclization product (36) (37%).
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菰田 泰夫, 金子 茂, 清水 正人, 山本 真沙子, 石川 正幸, 板井 昭子, 飯高 洋一
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From MeOH extract of Parazoanthus gracilis (Lwowsky), two anti-histamine active compounds, paragracine (1) and norparagracine (2), were isolated. The structure of (1) was determined from its chemical and spectral properties, and by X-ray crystallographic analyses of paragracine dihydrobromide and paragracine itself. The structure of (2) was elucidated by the comparison of its chemical and spectral data with those of (1). The biological activity of (1) was investigated by the various bioassay systems. The anti-Ach activity of the derivatives of (1) was also compared with that of (1).
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市原 耿民, 白石 久二雄, 小笠原 恵美, 佐藤 博二, 坂村 貞雄, 西山 幸司, 酒井 隆太郎
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Coronatine (1), produced by Ps. coronafaciens var. atro-purpurea, is the chlorosis-inducing toxin and also has an activity to expand potato cells in the concentration of 1×10^<-7> mole/1. Hydrolysis of coronatine affords a new amino acid, coronamic acid (5), and coronafacic acid which exist as two stereoisomers, 2a and 2b depending on the conditions of purification. On the bases of chemical and spectral data of coronatine and the degradation products, the chemical structure of coronatine has been shown to have an unique structure 1 hitherto unknown.
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山崎 幹夫, 藤本 治宏, 河崎 孝男, 奥山 恵美, 久我 哲郎
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In the course of our survey investigation of the toxigenic fungi found growing in foods and foodstuffs, some strains of Aspergillus fumigatus having a tremorgenic property have been found. By intraperitoneal administration of ethyl acetate extract of the fungus, experimental animals such as mice, rats or rabbits exhibited a sustained trembling with an intermittent convulsion. From the extract of the mycelia, four new indole compounds (FTA, B, C and D) were isolated. FTA and B were found to cause tremor to the animals but C and D were not. On the structure of fumitremorgin B (FTB), the presence of the 6-methoxy indole ring as a basic skeletone was first estimated and the structure was finally proposed as I from the spectral studies. The relative stereo-structure was subsequently determined by the X-ray analysis of FTB itself and the absolute configuration was determined based on that of proline obtained by hydrolysis of FTB. Fumitremorgin A (FTA) showed a closely resembled property to that of FTB in the spectral data and the structure was established as IV from the results of chemical and spectral studies on FTA and its derivatives. The structures of FTC and D were shown as XI and XIII, and they were named isotryptoquivaline and norisotryptoquivaline, respectively.
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丹羽口 徹吉, 中原 雄二, 井上 堯子, 林 誠, 石井 永
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Lysergic acid diethylamide(LSD) was transformed into lysergic acid ethylamide(LAE), norlysergic acid diethylamide(norLSD), lysergic acid ethyl, 2'-hydroxyethylamide(LEO) and lysergic acid ethyl, vinylamide(LEV) by incubation with Streptomyces roseo-chromogenes, St. fluvssimus, St. massasporeus, St. platensis, St. rimosus and St. lavendulae. LAE and norLSD have also been obtained by incubation of LSD with animal liver microsomes. LEO and LEV, new metabolites of LSD, are considered to be the key substances of metabolic de-ethylation pathway from LSD to LAE. LEV has also been produced by incubation with rat liver microsome and is considered to be a metabolic intermediate in the de-ethylation pathway of LSD. Incubation of lysergic acid dipropylamide with St. roseo-chromogenes gave two epimeric compounds of lysergic acid 2'-hydroxypropyl, propylamide, and lysergic acid acetonyl, propylamide. From the consideration of the results of microbial transformation of several amides of lysergic acid, the main metabolic conversion of amide branches is seemed to belong to a kind of an (ω-1)-oxidation pathway.
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伊藤 一男, 春名 光昌, 古川 宏
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The alkaloidal components of the leaves, trunks, roots and seeds of Erythrina plants (Leguminosae) were systematically examined. Twelve known alkaloids were isolated and characterized. In addition, four new non-phenolic bases, which were named erysotramidine (I), crystamidine (II), erytharbine (III) and 11-hydroxyerysotrine (IV) were isolated and their structures were respectively determined. It is interesting that the isolation of (I), (II) and (III) from Erythrina species is the first example of the natural Erythrina alkaloids containing an amide group. Although syntheses of 3-oxoerythrinan have been reported by many workers, their methods seem to be tedious or show low yields in some steps in the syntheses. In our synthesis of erythrinan, 1-[2-(3-hydroxy-4-methoxyphenethyl)]-3a,4-dihydro-1H-indole-2(3H), 6(5H)-dione (22) is an important key intermediate. We described here the easy preparation of this intermediate (22) from the enol methyl derivative (18), which was obtained by the Birch reduction of benzyl amide without cleavage of amide bond. (22) was refluxed in 98% formic acid for 16 hours to give a desired tetracyclic compound, C/D-cis-15-methoxy-16-hydroxy-3,8-dioxo-erythrinan (23)(65% yield). Reduction of (23) with lithium aluminum hydride in THE gave tetrahydroerysonine (30) and its epimer at C_3-hydroxy group. Moreover, i.r. and n.m.r. spectra of the O-methyl ether of (30) were completely superimposable on those of its authentic sample (32). For the short synthetic route and easy availability of starting compounds, we think that the method reported here may be suitable to use widely for the syntheses of Erythrina alkaloids.
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坂井 進一郎, 相見 則郎, 山口 啓一, 堀 こすみ, 萩庭 丈寿
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From Gardneria multiflora Makino (Loganiaceae) we have further isolated several new alkaloids. Structure elucidation of the six of them are presented. Alkaloid J (IX) and L (X) are trimethoxy oxindole alkaloids having gardneramine skeleton. The characteristic feature of these alkaloids is their C-16-R configuration, which was proved by formation of the ether ring between C-16 and C-20 on heating of IX or X in dilute hydrochloric acid. IX and X were derived from known bases gardneramine I and 18-demethylgard-neramine III respectively as shown in charts 1 and 3. Alkaloid N (XII) is also trimethoxy oxindole alkaloid which has glycol function at C-16 and C-17. This functionality was proved by formation of acetonide f. The configurations of C-7 and C-16 of XII were determined by generation of iminoether compound h via mesylate g. Gardneramine-N-oxide (XIII), alkaloid M (XI), exomethylene compound (XIV) were also isolated. Alkaloidal constitution of Gardneria liukiuensis was also studied, which was proved to be quite similar to that of Gardneria multiflora.
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石井 永, 原田 健一, 石田 俊明, 上田 悦子, 植田 美代子, 二宮 一弥, 内藤 猛章, 木口 敏子
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セッションID: 40
発行日: 1975/10/01
公開日: 2017/08/18
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For the structure of chelirubine three formulae [I-8(Slavik's), II-8(Ishii's) and III(Onda's)] were proposed. The compound having the formula (II-8) was prepared by using photocyclization of the enamide (34). The identity of the synthetic intermediate (37) with an authentic sample of oxychelirubine indicates that the structure of chelirubine should be depicted by the formula (II-8). This allows us to propose the correction of the structures of chelilutine, sanguirubine and sanguilutine to the formula (II-11), (II-12) and (II-(II-13) from (I-II), (I-12) and (I-13) proposed by Slavik, respectively. The structures of arnottianamide (38) and isoarnottianamide (41) were also established by transformation from chelerythrine (2) and nitidine (3) by means of Baeyer-Villiger type oxidation of an immonium group with peracid. We are interested in considering the possibility of formation of chelilutine (II-11) by recyclization of isoarnottianamide (41) in plant.
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亀谷 哲治, 福本 圭一郎, 井原 正隆, 根本 英雄
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セッションID: 41
発行日: 1975/10/01
公開日: 2017/08/18
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Some indole alkaloids have been synthesised by three methods; step by step synthesis, biomimetic type synthesis and retro mass spectral pattern synthesis. 4,6-Dimethoxycarbonyl-2-pyridone was converted into indolo[1,2-b]quinolin-9(11H)-one-7-carboxylic acid, whose methylation at C_8 with CH_2N_2, followed by conversion of methoxycarbonyl group into α-hydroxypropyl residue, gave mappicine. From a hypothesis that angustine would be biosynthesised from tryptophan and secologanin, angustine was synthesised by two routes from gentianine analogs which would be biogenetic equivalents to secologanin. On the basis of mass spectral fragmentation pattern of olivacine and yohimbine the former alkaloids could be synthesised from indole and 3,4-dibromomethyl-2-methylpyridine, and yohimbine from indolo-[2,3-a]quinolizin-2-one and 3-oxo-4-pentenoate. Moreover, the synthetic approach to the latter alkaloid by retro mass spectral pattern synthesis is also described.
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藤井 澄三, 吉藤 茂行
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セッションID: 42
発行日: 1975/10/01
公開日: 2017/08/18
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Condensation of 2-benzyloxy-3,4-dimethoxyphenacyl bromide (V) with ethyl trans-3-ethyl-6-methoxy-2,3,4,5-tetrahydro-4-pyridineacetate (VII) gave lactam ketone VIII, which on sequential reduction with NaBH_4 and catalytic hydrogenolysis afforded lactam phenol XI. The benzyl ether of XI was cyclized with POCl_3 and the resulting quaternary salt [XIII (X=Cl)] was hydrogenated to furnish tricycle XV. The LiAlH_4 reduction of XV followed by hydrogenolysis provided racemic ankorine [(±)-IV]. A parallel synthetic route starting with lactim ether VII and 3,4,5-trimethoxyphenacyl bromide yielded tricycle XIX via lactam ketone IX. The 9,10,11-trimethoxy derivative (XIX) thus obtained did not correspond to the O-methyl derivative of natural ankorine. These results have identified the structure and relative stereochemistry of ankorine as IV. Ethyl cincholoiponate [(+)-XX], prepared from cinchonine (XXII), with V and K_2CO_3 in benzene yielded (-)-XXIII, which on sequential reduction with NaBH_4 and oxidation with Hg(OAc)_2-EDTA gave XXV and a compound presumed to be its isomer (XXVI). Hydrogenolysis of XXV followed by benzylation, alkaline hydrolysis, and thermal isomerization furnished a hardly separable 63: 37 mixture of the trans-(XXX) and the cis-acid (XXIX). The mixture was, after esterification, cyclized with POCl_3 to a mixture of trans- and cis-XXXII. Catalytic hydrogenation of the mixture of the quaternary salts (XXXII) and chromatographic purification of the basic product gave (-)-XV, which on LiAlH_4 reduction followed by hydrogenolysis furnished (-)-IV, identical with natural ankorine. Thus, the "synthetic incorporation of cincholoipon into ankorine" described above has proved that stereoformula IV is a complete expression for ankorine.
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津田 喜典, 佐野 武弘, 多賀 淳一, 礒部 公明, 戸田 潤, 入江 寛, 田中 洋和, 高木 修造, 山木 正枝, 村田 まゆみ
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セッションID: 43
発行日: 1975/10/01
公開日: 2017/08/18
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There have been many reports aiming at synthesis of lycorine 41 which is the most wide-spread and common alkaloid occurring in Amaryllidaceae plants. In connection with our synthetic work of Amaryllidaceae alkaloids, we have now completed synthesis of lycorine. Treatment of the kown uethane-ester 14 with POCl_3 followed by SnCl_4 in CH_2Cl_2 gave the lactam 12 which was reduced to the alcohol 18. 18 was converted to the chloride 19, then cyclized into the tetracyclic lactam 21 via imino-ether 20. 21 was also obtained from the imide 17, which in turn was obtained from 12 via the acid 16 by reduction with LAH under strictly controlled condition in 80% yield. Oxidation of 21 with m-CPBA gave the α-epoxide 31 as a sole product. Ample supply of the lactam 21 and the epoxide 31 were provided from dihydrolycorine as shown in the text(28→29→30→32→21). The α-epoxide 31 on treatment with 5% H_2SO_4 in dioxane afforded the trans-diol 29 which regenerated dihydrolycorine 28 by LAH reduction. Osmolation of the lactam 21 gave the cis-glycol 34 which was converted to zephyranthine 35. Treatment of the epoxide 31 with diphenyldiselenide and NaBH_4 followed by oxidation with NaIO_4 resulted in 38 (isocaranine-lactam). Acetylation of 38 gave the acetate which was oxidized with m-CPBA to give the β-epoxide 39. Treatment of 39 with diphenyldiselenide and NaBH_4 followed by NaIO_4 in the same manner as the case of 31 furnished lycorine-lactam 40. Reduction of its diacetate with LAH gave lycorine 41.
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奥野 智旦, 沢井 功, 盛 義高, 鈴木 玲子, 松本 毅
原稿種別: 本文
セッションID: 44
発行日: 1975/10/01
公開日: 2017/08/18
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Alternariolide 1 was one of the unique toxic principles from the title fungus. The new amino acid (named alternamic acid) which is one of the components of 1, 2-amino-5-(p-methoxy phenyl)-pentanoic acid, was prepared from α-(p-anisyl)-butyric acid. In order to synthesize 1, two depsipeptides, Z-alternamyl-L-seryl-L-alanyl-L-α-hydroxyisovaleric acid tert-butyl ester 13 and α-THPoxy-isovaleryl-alternamyl-seryl-alanine methyl ester 17, were prepared. Experiments of cyclization and dehydration of the serine moiety of the peptides are now in progress.
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