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児玉 久, 藤森 嶺, 加藤 邦雄
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Three new sesquiterpene glycosides, 3-hydroxy-solanascone-β-sophoside (1), rishitin-β-sophoroside (5) and 3-hydroxy-solavetivone-β-glucoside (8) were isolated from flue-cured tobacco. The structure of (1) was elucidated by two dimensional NMR (2D NMR) spectra of its acetate (2). On the COSY 45N spectrum, the W type long range coupling was observed between H-10α and H-11α. In addition to the usual W type interactions, 1,3 diaxial coupling between H-3 and H-5 was resolved in the 2D J spectrum. Relative configuration was elucidated by the nuclear Overhauser effect (NOE) differential spectrum. The aglycone of (1) was 3-hydroxy derivative of solanascone which was characterized as stress compound. The structures of (5) and (8) were elucidated by the application of ^1H NMR and ^<13>C NMR. The aglycones of these glycosides, (5) and (8) were characterized as stress compounds. Antibacterial activities of these glycosides, (1), (5), (8), and sesquiterpene, solavetivone (10), solanascone (4), rishitin (7), 3-hydroxysolavetivone (9), were examined against a virulent strain of Pseudomonas solanacearum. The antibacterial activities of the glycosides were not detected, but the sesquiterpenes showed the activities at 2-5μg/spot.
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広野 巌, 大場 茂, 斉藤 喜彦, 丹羽 治樹, 小鹿 一, 若松 一雅, 山田 静之, 松下 和弘
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We have examined the constituents of bracken fern, Pteridium aquilinum var. latiusculum and performed fractionation of the boiling water extracts by means of the assay based on carcinogenicity to rats. From the fraction exhibiting carcinogenicity, we have isolated an unstable norsesquiterpene glucoside of illudane type named ptaquiloside (1). The planar structure of (1) has been established on the basis of spectral and chemical means. The carcinogenicity of (1) to rats is currently under investigation.
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森田 雅哉, 加藤 夏樹, 岩下 孝, 中西 香爾, G. Savona, F. Piozzi
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Teucrin P1 1 isolating by Popa', Mollov', and Piozzi's groups showed specific rotations of [α]_D +22.4, 6.6, and -13°, respectively. Piozzi's group reported X-ray study on its absolute stereochemistry and conformations which retained a boat form on B ring. However, we found that the boat form was an unstable conformation than the chair form by about 1 Kcal/mol with molecular mechanics. Then we attempted to derive a conformational isomer 4 (B ring: chair) from 1 and to analyze its conformation by CD and NMR spectra. The isomer 4 was given as needles by treatment with LDA/HMPA-THF followed by purification on pTLC and recrystallization from ether-acetone, and showed CD spectra (Fig. 3, 6) and [α]_D +2.93°different from 1. However, the isomer 4 reproduced 1 by recrystallization from EtOAc-hexane. These facts show that the B ring of 1 retaines the boat form as the stable conformation by solvation. Teucrin P1 1 attained to equilibrium with 4 content of ca. 30% after 5 days in CHCl_3 at 0℃. On the other hand, it is very significant that the isomer 4 decrease to about 75% content after 84 hrs in CHCl_3 at 25℃ (Fig. 8). It was unexpected that NMR spectra (2DJ, 2DNOE, and differece NOE spectra) of 4 were almost identical to those of 1. Differences on the spectra between 1 and 4 were shown only by coupling patterns of higher orders for the signals at 2.88 (C・7 Hβ) and 2.20-2.30 (C・7 Hα, C・8 H) ppm (Fig. 10). Now we propose that Teucrin P1 presents with the chair conformation in both native plants, and the conformation changes in the process of the extraction and recrystallization.
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大東 肇, 廣田 満, 大塚 隆尚, 小清水 弘一, 徳田 春邦, 伊藤 洋平
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The Epstein-Barr virus (EBV) is a ubiquitous viral agent known to be distributed among humans and suspected to be intimately associated with Burkitt's lymphoma and nasopharyngeal carcinoma. Recently the EBV activity has been shown to be induced by several chemicals and the EBV inducing agents in our environment have come to be recognized as a serious problem. Throughout our continuous screening of plant extracts against the EBV induction, active constituents of two plant species, Sapium sebiferum (Euphorbiaceae) and Edgeworthia papyrifera (Thymelaeaceae), which are very familiar to us as a roadside and garden tree, and a raw material of Japanese traditional paper, respectively, have been investigated. Three active principles, isolated from the leaves of S. sebiferum, have been identified as tigliane type esters, 12-O-hexadecanoyl-phorbol-13-acetate (1), Δ-5,6-7β-hydroperoxy derivative (2) and Δ-5,6-7-one derivative (3) of 1. Two active principles, 8 and 9, isolated from the stems of E. papyrifera, have been characterized as intramolecular orthoesters formed from parent polyhydroxy-acids, oxygenated derivatives of 1α-alkylresiniferonol-ω-oic acids. 1, 2, 8 and 9 highly induced the EBV early antigen in Raji cells. Of the four constituents, the activity of 9 was higher than that of TPA (12-O-tetradecanoyl-phorbol-13-acetate), known to be the most potent tumor promoter.
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石塚 みどり, 楠見 武徳, 柿澤 寛, 川上 善之, 永井 泰志, 里 忠
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The brown alga, Pachydictyon coriaceum, produces various type of diterpenes such as 1-4. Chromatographic separation of the methanol extract of this seaweed afforded six new diterpenes, 7, 8, 14, 17, 18, and 19. Acetylcoriacenone (7) is a novel diterpene, which possesses a unique cyclobutenone moiety. Its structure has been deduced on the basis of the spectral data, as well as chemical conversions. Auto-oxidation of 7 gives an epoxide 10, the stereochemical features of which have been elucidated as 12 by the analysis of the 400MHz ^1H-NMR spectrum. Isoacetylcoriacenone (8) is a C-19 epimer of 7. Pachylactone (14) includes a cyclopropane moiety, and its conformation has been deduced as in 15 from its characteristic ^1H-NMR spectrum; the methine proton at C-6 shows the unusual upfield signal at δ 0.85, shielded by both of C_1=C_2 and the cyclopropane ring, and also the signal due to H-10 in the side chain appears at δ 2.33, de-shielded by C=O at C-18, which shows that rotation about C_9-C_<10> axis is restricted so that 10-H is located close to the carbonyl group. Detection of NOE's between H-4b and H-19b, and between H-7a and H-9 supports the conformation 15. The structures of three other new diterpenes, 17, 18, and 19, have been elucidated by spectroscopic analyses.
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中谷 宗弘, 高尾 秀樹, 長谷 綱男, 直木 秀夫, 岩下 孝
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The root bark of Evodia grauca Miq. (Rutaceae) has yielded a series of new bitter limonoids, graucin A, B and C, with limonin and rutaevin. Extensive ^1H NMR studies including Homonuclear J-correlation techniques allowed us to assign all of the peaks in the complex spectra and derive the structures: graucin A; 12α-hydroxylrutaevin, graucin B; 6α-acetoxyllimonin and graucin C; limonin diosphenol. NOE difference spectra of limonin exhibited that irradiation of the axial 8β-Me peak induced 13.5% NOE in 15α-H signal. Similar NOE in 15-H signal was also observed in another limonin-type compounds.
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韓 徳龍, 金 貞姫, 笠井 良次, 水谷 健二, 谷保 樹典, 大谷 和弘, 田中 治
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1) A new ester-type glycoside, named chiisanoside(1) was isolated from stem bark of Acanthopanax chiisanensis(Araliaceae), a Korean folk medicine. On enzymic hydrolysis, 1 yielded a genuine aglycone named chiisanogenin(2), while mineral acid hydrolysis of 1 gave glucose, rhamnose and a modified aglycone(15). The sturcture of 2 was revealed by means of NMR spectrometry and chemical derivation in comparison with those of A-seco-betulinic acid(6) and its derivatives, and 1 was formulated as α-rhamnopyranosyl(1→4)-β-glucopyranosyl(1→6)-β-glucopyranosyl ester of 2 (Chart 1). 2) In part of our studies on the NMR of 2-linked arabinopyranosides, β-D-glucopyranosyl(1→2)- and α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranosyl esters of 3-O-acetyloleanolic acid(16) and caprylic acid(17) were prepared using tert-butyl as a new protecting group of a terminal anomeric OH. As already observed for platycodins etc., the anomalous NMR signals of the esters of 16 indicated the remarkable increase of contribution of ^1C_4 form of its arabinopyranosyl ring especially for the α-rhamnosyl-α-arabinosyl ester, while the NMR signals of the esters of 17 showed no unexpected displacement, demonstrating little contribution of the ^1C_4 form (Table 4). 3) It was found that LiI and 2,6-lutidine in methanol cleaved selectively an ester-glycoside linkage without any undesirable change of a sugar moiety, affording a methyl oligo-glycoside from an ester type sugar unit in a high yield (Chart 7).
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岡野 正義, 藤田 智之, 近藤 勝彦, 荒谷 孝昭
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1) Seven novel quassinoid glycosides named picrasinoside-A(4), -B(5), -C(6), -D(7), -E(8), -F(9), and -G(10) have been isolated from the barks of Picrasma ailanthoides PLANCHON, and their structures were established from spectral evidences, enzyme hydrolysis, chemical transformations into known compounds, and/or interconversion reactions. 2) Sugar linkage of each glucoside was revealed to be β-linkage by the way of coupling constant of each anomeric proton and/or enzyme hydrolysis using (β-glucosidase. 3) Configulation of β-D-glucose moiety in each glucoside except picrasinoside-A was confirmed as α-linkage from the coupling constant or half width of each acetal proton. 4) Picrasinoside-A and -B showed weak antitumor activity against P-388 lymphocytic leukemia cells in vitro, although the aglycon of picrasinoside-A showed a significant clastogenic activity in cell cultures of Don lung cells of Chinese hamster. Antileukemic activity test of the other glucosides is in progress.
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藤本 治宏, 鈴木 久美子, 田中 秀美, 山崎 幹夫
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The neurotropic and lethal toxicity to mice of Hebeloma vinosophyllum (Cortinariaceae) was observed by intraperitoneal administration of its aqueous methanolic extract. Both fruit-bodies of natural and cultured H. vinosophyllum were proved to be toxic, but extracts of vegetative mycelia obtained from shaking and stationary cultures in the dark were nontoxic. This fact indicated that the toxic metabolites might be produced after the formation of fruit-bodies in this mushroom. Solvent fractionation followed by repeated column chromatography of the aqueous methanolic extract of H. Vinosophyllum afforded three toxic principles, which were new compounds named hebevinosides I, II, and III. These compounds were estimated to have the triterpene glycoside structures from their chemical and spectral data. Acid hydrolysis of hebevinoside I(1) afforded an aglycone having heteroannular diene structure(3). The spectral data on 3 indicated that this compound has the cucurbitane skeleton. Although 1(lanostane-type) and 1a(cucurbitane-type) could be proposed as the possible structures for hebevinoside I to afford 3 on the acid hydrolysis, 1 was finally considered to be more likely than la, since a number of lanostane-type triterpenes have so far been isolated from the fungal species but the cucurbitane-type triterpenes have exclusively been found in the higher plants. From the same reason, 20 and 21 were also proposed to hebevinoside II and III, respectively.
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横田 孝雄, 馬場 淳, 有馬 昌広, 森田 誠, 高橋 信孝
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Seven new steroids which have plant growth-regulatory activity were isolated from plant sources, that is, dolicholide (4), dolichosterone (5), homodolicholide (8) and homodolichosterone (9) from immature seed of Dolichos lablab, 6-deoxocastasterone (3) and 6-deoxodolichosterone (6) from immature seed of Phaseolus vulgaris cv. Kentucky Wonder and 2-deoxycastasterone from pollen of Pinus Thunbergii. The structures of these compounds were determined by mass spectrometry and 400MHz ^1HNMR. In addition, 2 was isolated from Pinus pollen and GC-MS analyses revealed the presence of 1, 2, 3 and 6 in Dolichos seed and of 2 and 4 in Phaseolus seed.
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菊池 徹, 門田 重利, 松田 暁子, 末原 久
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Methylsterol components of Nervilia purpurea (I-tiam-hong), an Orchidaceous plant, were examined. The sterol fraction obtained from the neutral portion of the etherial extracts was purified by silica gel chromatography followed by preparative HPLC to give four new methylsterols, designated as cyclonervilasterol (1a), 24-epicyclonervilasterol (2a), dihydrocyclonervilasterol (3a), and 24-epidihydrocyclonervilasterol (4a), and their structures were determined based on the chemical and spectroscopic evidence. These sterols are unique in the structural feature having a cyclopropane ring at C_5-C_<10> positions. The stereochemistry at C_<24> position was assigned on the basis of the chemical shifts of the methyl groups in the ^1H-NMR spectra. Also the ^<13>C-NMR spectra were analysed in detail and the assignments of their carbon signals were done on the basis of INEPT and 2D-NMR methods.
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山田 幸子, 中山 恵子, 大森 正幸, 高山 浩明, 新木 敏正, 泉 芳子, 須田 立雄
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Metabolism of vitamin D_3 in vitamin D-supplemented state was studied and five new metabolites, 25-hydroxy-24-oxovitamin D_3, 23,25-dihydroxy-24-oxovitamin D_3, 23,24,25-trihydroxyvitamin D_3, 1,25-dihydroxy-24-oxovitamin D_3, and 25-hydroxyvitamin D_3 26,23-lactol, were isolated and identified. A new metabolite isolated from incubation mixture of 25-hydroxyvitamin D_3 with kidney homogenates from vitamin D-supplemented chicks was identified as 25-hydroxy-24-oxovitamin D_3. 25-Hydroxy-24-oxovitamin D_3 was metabolized further to three major metabolites in the kidney from vitamin D-supplemented chicks. They were isolated and identified as 23,25-dihydroxy-24-oxovitamin D_3, 23,24,25-trihydroxyvitamin D_3, and 24S,25-dihydroxyvitamin D_3. In the kidney from vitamin D-deficient chicks, 25-hydroxy-24-oxovitamin D_3 was converted to three major metabolites which were isolated and identified as 1,25-dihydroxy-24-oxovitamin D_3, 1,24,25-trihydroxyvitamin D_3, and 24S,25-dihydroxyvitamin D_3. On the basis of the results, the pathway 24R,25(OH)_2D_3→25(OH)-24-oxo-D_3→23,25(OH)_2-24-oxo-D_3 was suggested as the route leading to side chain cleavage. 25-Hydroxyvitamin D_3 26,23-lactol, a biosynthetic precursor of 25-hydroxyvitamin D_3 26,23-lactone, was isolated and identified from incubation mixture of 23S,25R,26-trihydroxyvitamin D_3 with kidney homogenate from vitmain D-supplemented chicks. Metabolites of vitmain D_3, 25-hydroxy-24-oxovitamin D_3, 23S,25R,26-trihydroxyvitamin D_3, and (23S,25R)-25-hydroxyvitamin D_3 26,23-lactol, were synthesized conveniently and stereoselectively.
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高瀬 茂弘, 川合 吉夫, 伊藤 義邦, 内田 逸郎, 堀合 東雄, 石見 盛太, 岡本 正則, 吉田 啓造, 田中 洋和
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In the course of our screening program for biologically active principles from fermentation sources, a novel alkaloid WF6237 (designated as amauromine) with vasodilating activity was isolated from Amauroascus sp. No. 6237. The structure of amauromine was determined to be 1a by means of chemical and spectroscopic evidence. Total synthesis of amauromine was also investigated. First, a model compound, debromo-8,8a-dihydroflustramine C 17 was synthesized by taking advantage of thioclaisen rearrangement reaction followed by ring closure with desulfurization by NaH. Syntheses of amauromine 1a and tetra-hydroamauromine 2 were achieved starting from L-tryptophan. The key intermediate 29 was obtained by simultaneous thioclaisen rearrangement reaction at the two centers on 28. Amauromine 1a was synthesized by desulfurization with low valent titanium reagent on 29, though the yield was low. Synthesis of tetrahydroamauromine 2 was accomplished by reduction with modelately activated Ra-Ni on 30. To our knowledge, this is the first synthesis of natural product containing reversed isoprenoid unit at C-3 of indole skeletone.
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石井 永, 川鍋 恵理, 関 宏子, 山口 啓一, 赤須 通範, 小玉 一哉, 國友 順一, 古川 宏, 鈴木 真言, 原田 健一, 武田 ...
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I) In order to prepare whole-body autoradiograms of experimental animals after drug administration, [methylenedioxy-^<14>C] cepharanthine was prepared. Cepharanthine was treated with BCl_3 in CH_2Cl_2 to give demethylenated cepharanthine in good yield. After non-radioactive experiments, treatment of three molar demethylenated cepharanthine with CsF and ^<14>CH_2I_2 in DMF gave [methylenedioxy-^<14>C]cepharanthine quantitatively. (The yield was calculated based on ^<14>CH_2I_2). II) The structures of four new secobisbenzylisoquinoline alkaloids (Base J, Base K, Base B, and Base C) which were naturally occurred in Stephania sasakii (Menispermaceae) were established. Secocepharanthine (Base J) and O-methylpunjabine (Base K) were derived by controlled oxidation of cepharanthine and of isotrilobine, respectively, including a sign of optical rotation. Treatment of secocepharanthine with NaBH_4 gave dihydrosecocepharanthine (Base B). Wolff-Kishner reduction of O-methylpunjabine gave O-methyldeoxopunjabine (Base C). III) The bisbenzylisoquinoline alkaloids belong to a type of oxyacanthine-berbamine are subdivided into oxyacanthine- (cis O_4-O_4), repandine- (trans O_4-O_4), berbamine- (cis O_5-O_3), and tetrandrine- (trans O_5-O_3) groups. In order to examine the effect of their conformations in an eighteen membered ring to reaction behavior in detail, their PMR and ^<13>C-NMR spectra were systematically measured. Following conclusions will be discussed: The oxyacanthine type alkaloids (cis O_4-O_4) bearing a methoxy group at C_7 position are present as atropisomers between 8,7'-biaryl ether in a CHCl_3 solution at room temperature. In all of these four type alkaloids, their N-methyl groups at the N_<(2)> position were situated in axial. In the PMR spectrum, the signal due to the C_<10>,-aromatic proton appeared in the high field, around δ 5.5. The assignment of signals in the ^<13>C-NMR spectra of these alkaloids will be shown.
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中川 正, 遠藤 衛, 田中 信夫, C. P. Lee
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Four coronary vasodilative compounds, Xestospongin A(1), Xestospongin B(2), Xestospongin C(3) and Xestospongin D(4) have been isolated from 100% EtOH extract of the lyophilized marine sponge, Xestospongia exigua, which was collected at the adjioining seas of Hook Island of Queensland in Australia. The structure of Xestospongin C(3) have been elucidated by spectral study and X-ray crystallographic analysis. The other structure of Xestospongins have been established by the comparison with the spectral data of Xestospongin C(1). New type of macrocyclic 1-Oxaquinolizidin, Xestospongins which shows a strong coronary vasodilative effects at the cocentration of 5μg/heart (ED_<50>).
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中村 英士, 呉 厚銘, 阿部 玲子, 小林 淳一, 大泉 康, 平田 義正
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Numerous marine natural products with biological activities have been isolated from various marine organisms. It has been expected that chemical substances possessing useful pharmacological actions will be obtained from marine organisms. We have examined pharmacological actions of 70% ethanolic extracts of various sea sponges collected at Okinawa using several isolated muscle preparations. Extracts of the sea sponge Aaptos aaptos showed an α-adrenoceptor blocking activity on the isolated rabbit aorta and a novel tricyclic heteroaromatic substance, aaptamine 1a has been isolated from the sea sponge as an active principle by monitoring the activity. In addition, the related substances, demethylaaptamine 1b and demethyloxyaaptamine 2 have been isolated from the sponge as antimicrobial substances. The orange sea sponge Agelas sp. gave extracts showing an antispasmodic activity on the isolated guinia-pig ileum and a novel sesquiterpene, agelasidine-A 7 has been isolated from the sea sponge as a main active component. Furthermore, from the brown sea sponge Agelas sp. a new bromopyrrole substance, keramadine 11 has been isolated as an antiserotonergic substance monitored by the activity on the isolated rabbit aorta. The structures of these active substances have been determined on the basis of the spectral data and chemical degradation experiments.
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福山 愛保, 三浦 巌, 金城 順英, 中山 康夫, 高橋 真行, 木戸 勝
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In the course of our search for an anti-plasmin inhibitor, new polyhydroxydibenzo-p-dioxins named eckol (1), 6,6'-bieckol (2), 8,8' bieckol (3), dieckol (4) and 2-phloroeckol (5) have been isolated from the methanol extract of a brown alga Ecklonia kurome Okamura. They have been found to have strong inhibitory activities on plasma plasmin inhibitors; α_2-macroglobulin and α_2-plasmin inhibitor. Their structures were elucidated to be 1, 2, 3, 4 and 5 by means of extensive NMR analyses and other spectroscopic data. NIP (negative induced polarization) effect, in particular, was proved to be a valuable tool to determine the arrangement of hydroxy groups on the benzene nucleus. The compounds 1-5 could be the first examples of the naturally occurring phlorotannin having dibenzo-p-dioxin skeleton. It is worth of note that all the polyhydroxydibenzo-p-dioxins described herein exhibit strong inhibitory activities on plasmin inhibitors, whereas phloroglucinol, triphloroethol (6) and diphloroethol (7) not carrying 1,4-dioxane ring possess no activity.
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姚 新生, 海老塚 豊, 野口 博司, 木内 文元, 飯高 洋一, 三川 潮, 瀬戸 治男
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As a continuation of our studies on biologically active compounds contained in traditional medicinal drugs, we have investigated inhibitors of Prostaglandin(PG) biosynthesis contained in "Nan-Shikon", the root of Arnebia euchroma. In our previous screening, hot aquous extracts of "Nan-Shikon" showed significant inhibitory activity against PG synthesizing enzyme system prepared from rabbit renal medulla microsomes. It was found, however, that naphtha-quinones known as the main constituents of "Nan-Shikon" was not contained in the hot water extracts, so that the PG biosynthesis inhibitors would be different from the compounds isolated from "Nan-Shikon". Partition with solvent followed by repeated chromatography finally gave inhibitors of PG biosynthesis tentatively designated as NS-2(1), 3(2), 4(3), 6(5) and 7(4). NS-2(1) was identified to be a mixture of shikonofuran B and C which had been isolated from "Ko-Shikon", the root of Lithospermum erythrorrhizon. NS-7 was identified as de-O-methllasiodiplodin isolated formerly from a fungus, Lasiodiplodia theobroma. A question remains unsolved whether NS-7(4) is produced by the plant or by the contaminated fungi. The spectral data of NS-4(3) suggested that it is a new compound and a dehydroderivative of geranylhydroquinone. The structure of NS-4, named arnebinol, was finally established by X-ray crystallography as a new ansa-type monoterpenyl benzenoid. NS-6(5) is a orange coloured compound and its UV spectrum suggested it being a benzoquinone derivative. Structure investigation finally led to the conclusion that NS-6, named arnebinone, is a new monoterpenoid benzoquinone possessing a fused 6 membered ring arising from successive migration and cyclization of geranylhydroquinone. Inhibitory activity against PG biosynthesis is stronger in NS-7 and 2 than in NS-4 and 6. Structure of NS-3 which showed similar colour with NS-6 is under investigation.
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松原 義治, 隈元 浩康, 飯塚 義富, 村上 哲男, 岡本 耕造, 三宅 英夫, 横井 勝美
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The structure of flavanoid and flavonoid glycosides isolated from hot water extract of lemon(citrus lemon burum f.), satsuma mandarin(citrus unshiu Marc.), grape fruit(citrus paradisi Macf.) and kinkan(citrus japonica M.) peels were investigated and the tests of their physiological activities were attempted on stroke-prone spontaneously hypertensive rat(SHR-SP). Separation and purification of the flavanoid and flavonoid glycosides of four citrus fruits were attempted on the hot water extract-solvent extract-precipitation method by lead subacetate-gel filtration on TSK gel HW40-F-column chromatography on silica gel by a characteristic solvent system. Eleven constituents [L-1]〜[L-11] from lemon, ten constituents [U-1]〜[U-10] from satsuma mandarin, six constituents [G-1]〜[G-6] from grapefruit and seven constituents [K-1]〜[K-7] from kinkan were isolated and each glycosides was determined on the basis of its MS, UV and NMR spectra and chemical evidence. Each component was measured chronologically using the tail-puls pick up method without anesthesia. Thus [L-2], [L-3], [L-4] and [L-7] from lemon; [U-1], [U-3] and [U-10] from satsuma mandarin; [G-1] and [G-3] from grapefruit; [K-2] and [K-3] showed (especially) marked falls of blood prussure after interavenous administration.
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深井 俊夫, 羽野 芳生, 幾田 尚人, 藤本 朝子, 平倉 一弘, 野村 太郎, 鵜沢 洵, 小松 一男, 福島 和貴
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From the Chinese crude drug "Sang-Bai-Pi" (Japanese name Sohakuhi), the root bark of Morus sp., two new flavanones were isolated and named sanggenon G (I) and kuwanon L (IV). On the other hand, kuwanons K (II), L (IV), N (III), O (V) and P (IX) were isolated from the Japanese root bark. The structures were shown with chemical and spectral data. These compounds are regarded biogenetically as Diels-Alder adducts of chalcones and dehydroprenyl (or geranyl) phenol derivatives. Mulberrofurans F (X), G (XI), H (XII), I (XIII) and kuwanon M (VIII) were also isolated from Japanese root barks. These compounds seem to be oxidation products of such Diels-Alder adducts or a Diels-Alder adduct of prenylflavone and dehydroprenylflavone. Conformational isomers of some Diels-Alder adducts are discussed with ^1H relaxation times (T_1) of sanggenons C (VI) and D (VII).
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吉田 隆志, 波多野 力, 奥田 拓男, M. U. Memon, 新宮 徹朗, 井上 謙一郎, 福島 和貴
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New way of applying ^<13>C-NMR and MS spectra for the structural assignments of oligomeric hydrolyzable tannins have been developed. (I) The FAB-MS measurements of several monomeric and dimeric hydrolyzable tannins proved that FAB-MS can be applied for the determination of the molecular weights of these tannins without derivatization. (II) Full assignments of the glucose carbon signals of hydrolyzable tannins in the ^<13>C NMR spectra have been accomplished by {^1H}-^<13>C selective decoupling. These results gave following conclusions. (a) The peak sequences of carbons in glucose are different among several types of hydrolyzable tannins, reflecting the difference of acyl (galloyl, HHDP and DHHDP) groups on the ^4C_1 glucopyranose ring, as found upon comparison of penta-O-galloyl-β-D-glucopyranose (5), casuarictin (11), tellimagrandin II (17) and isoterchebin (19). (b) The additive parameters of galloylation and hexahydroxydiphenoylation shifts can be used for locating the position of acyl group. (c) The substituents and substitution mode at C-1 and C-2 of glucose core can be deduced based on the ^<13>C chemical shift of the anomeric carbon signal. (d) The ^<13>C resonances of the oligomeric hydrolyzable tannins can be assigned on the basis of the data for their monomeric units.
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藤本 康雄, 高橋 達之, 横山 栄藏, 鵜沢 洵, 角田 広, 辰野 高司
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Three new trihydroxynaphthalenones(PD-2, PD-3 and PD-4) have been isolated from the culture filtrate of P. diversum var. aureum together with three known naphthalenones, sclerone(PD-5), isosclerone(PD-6) and juglone(PD-7), and herqueinone(PD-1), major metabolite of this fungus, has also been isolated from the mycelium. The structure of PD-3 was determined on the basis of its chemical properties and the spectroscopic analyses on PD-3 methylether(Ia) and PD-3 dimethylether(Ic). The ^1H-NMR decoupling experiments on Ia revealed the presence of the partial structures A and B. Finally, the structure of PD-3 was confirmed by the application of the ^<13>C-^1H long range selective proton decoupling experiments on its dimethylether which was obtained from PD-3 by the action of diazomethane. The structures of PD-2 and PD-4 were also determined by comparison of their ^1H-NMR data with those of PD-3, PD-5 and PD-6. PD-2, PD-3 and PD-4 showed cytotoxity against Yoshida sarcoma cells in tissue culture at 20-50mcg/ml respectively.
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末光 力作, 佐野 友彦, 有本 禎男
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The structure of new red pigment, alterporriol B, isolated from culture broth of Alternaria porri (Ellis) Ciferri, the fungus causing black spot disease of stone-leeks, was elucidated. Comparing its chemical and physical properties and spectral data with those of Altersolanol A (VII) and macrosporin (III), alterporriol B was supposed to be an anthraquinone dimer consisting of altersolanol A and macrosporin moiety. This assumption is well accord with the fact that (II), (III), and (IV) were obtained on the reductive decomposition reaction with Na_2S_2O_4. Considering the results of ^1H-NMR spectra, alterporriol B is probably bonded at 8-8' position of altersolanol A and macrosporin respectively.
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塚本 博樹, 久田 末雄, 西部 三省
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This paper deals with the isolation of the new lignans related to (+)-pinoresinol from Oleaceae plants and their structure determination 1. Phillygenin(1), (+)-pinoresinol(2), phillyrin(3) and (+)-pinoresinol-β-D-glucoside(4) were isolated from the fruits of Forsythia suspensa Vah1 and F. koreana Nakai. (+)-Epipinoresinol-4"-β-D-glucoside(6) was obtained from the bark of F. suspensa collected in Germany. The structures of 1, 3 and 6 were established by the spectroscopic analysis based on ^<13>C-NMR. 2. (+)-1-Acetoxypinoresinol(8) and related compounds 10, 12 and 13, (+)-1-hydroxypinoresinol(9) and related compounds 11, 14 and 15, and (+)-fraxiresinol-1-β-D-glucoside(16), along with known lignans 17 and 18, were isolated from the bark of Olea europaea L. Their structures were elucidated by the spectroscopic analysis based on ^<13>C-NMR and chemical evidence. Further, lignans from the bark of Olea species were investigated to isolate 8, 9, 10, 12, 13 and 19 from Olea africana Mill., and 17 and 18 from Olea capensis L. 3. (+)-Fraxiresinol(20) and (+)-1-hydroxysyringaresinol(21), in addition to 2, 4, 9, 17 and 18, were isolated from the bark of Fraxinus mandshurica Rupr. var. japonica Maxim. Their structures were elucidated by the spectroscopic analysis based on ^<13>C-NMR and chemical evidence. Also, lignans 2, 4, 9, 14, 17, 18 and 20 were isolated from the bark of Fraxinus japonica Blume.
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高橋 寛治, 森 達哉, 柏原 正人, 上村 大輔, 片山 忠二, 岩垂 秀一, 志津里 芳一, 三友 隆司, 中野 文夫, 松崎 明紀
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Oxazolomycin is a new antitumor antibiotic isolated from Streptomyces sp. (Y-32026). The structural elucidation of this non-crystalline antibiotic has been carried out. Its structure has been determined as shown in 1 on the basis of spectral analysis, X-ray crystallographic analysis or synthesis of corresponding degraded products. Our interests have been focused on not only its novel structure exemplified as the β-lactone functional groupings but also the structure-activity relationship. Therefore, in vitro direct cytotoxicity of oxazole derivatives and each segment of oxazolomycin has been examined. Based on some obtained results, the structure-activity relationship of oxazolomycin will be discussed. Isolation and strcutures of two minor congeners will be also reported.
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瀬戸 治男, 降旗 一夫, 大岳 望, 伊藤 泰博, 高橋 秀次, 羽石 達生
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By use of new NMR techniques, in particular, long range J-resolved 2D NMR (LRJR), the structure of oxirapentyn, which is an antibiotic produced by Beauveria felina, has been established as shown in Fig. 8. LRJR has proved to be a very powerful method to analyzed ^<13>C-^1H long range couplings and will become one of the most important methods for structural elucidation of natural products.
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林 紘司, 中川 喬, 和田 啓爾, 吉村 慎一, 塚本 佐知子, 成田 弘美, 三橋 博
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During the course of our studies on the biologically active asclepiadaceous glycosides, several oligosaccharides were isolated from hydrolysate of the glycoside which showed positive Keller-Kiliani reaction due to 2-deoxysugar contained. Four new oligosaccharides: neocondurangotriose from Condurango Cortex, dregeatriose from Dregea volubilis, glaucobiose from Cynanchum glaucescens, and wilforibiose from C. wilfordi were elucidated to have the structures (14), (15), (11), and (12) respectively on the bases of chemical and spectroscopic data. Characteristic glycosidation shifts were observed among the 2,6-dideoxysugars and the related oligosaccharides and glycosides. These shifts seemed to be separated into two categories which are ascribed to the orientation of the substitution of the ProR(β)carbon in Fig. 6.
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西沢 麦夫, 足達 健二, 林 雄二, S. Sastrapradja
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Cyanolipids are a unique group of plant lipids classified into four types I-IV, characteristic to seed oil of Sapindaceous plants. This interesting class of lipids has never been purified completely and structual discussions have always been carried out using mixtures, since most of the cyanolipid mixtures behave like a homogeneous component on chromatographic or spectral study. We have succeeded the first purification of the major three kinds of type II cyanolipids N-IIb, N-IIc, and N-IId of Nepherium lappaceum by using reverse phase HPLC, and established the full structure to be 1b, 1c, and 1d, respectively. Recent discovery of the insecticidal activity of cyanolipids prompted us to design a general synthesis of this class of natural products. Thus, a very simple procedure using phase-transfer catalyst (solid-liquid) has been developed, and three kinds of the type II (1b, 1c, and 1d) and three kinds of the type III (2b, 2e, and 2f) lipids have been prepared together with more than twenty artificial analogs. Biological examinations of these synthetic products are examined using hatched larvae of insect pests of American cotton field.
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菊地 博之, 築谷 康柾, 井口 和男, 山田 泰司
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In connection with our continuing studies on the biologically active constituents of Japanese marine organisms, we have isolated new type of prostanoids, clavulone I(1), II(2), III(3), IV(4) and their congeners 5-8, from the Stolonifer Clavularia viridis Quoy and Gaimard. The structures of these compounds have been elucidated on the basis of spectroscopic data and chemical reactions. Reduction of clavulone I(1) with NaBH_4 gave an alcohol 9, which was oxidized with PCC to give an α,β,γ,δ-unsaturated ketone 11 (Chart 1). Ozonization of 1 gave two aldehydes 12 and 13 (Chart 1). These chemical reactions and analyses of spectral data established the plane structure of clavulone I. Catalytic hydrogenation of 1-3 (Chart 2) and acid-catalyzed isomerization of 1 gave the evidence that 1-4 are the geometrical isomers at carbon-carbon double bonds each other having the same carbon skeleton and oxygen functionalities including the absolute configuration. The geometry of the carbon-carbon double bonds at C-5, -7 and -14 were determined by the ^1H-NMR chemical shifts and coupling constants of the olefin protons as shown in Fig.1. The absolute configuration at C-4 for 1-4 was determined as R by transforming the aldehyde 13 into the lactone 16. The 12-R configuration was elucidated by disclosing the relative stereochemistry (cis) between the C-12 acetoxyl group and C-9 hydroxyl group in 20 on the basis of the presence of intramolecular hydrogen bond between these groups, and then by determining the absolute stereochemistry at C-9 in 9 using exciton chirality method in CD spectrum of 18 (Fig. 2). The structures of 5-8 were determined by comparison of their spectral data with those of 1-4.
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小林 資正, 安澤 亨, 吉原 実, 孫 炳華, 李 南庚, 北川 勲, 木戸 勝, 京極 好正
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During the course of studies in search of bioactive marine natural products, we have investigated the chemical constituents of two stolonifers: Clavularia viridis and C. koellikeri (Coelenterata, Anthozoa, Octocorallia, Stolonifera, Clavulariidae), which were collected in the coral reefs of Okinawa waters. This paper provides the evidence which substantiates their absolute stereostructures. 1) Anti-tumor active new prostanoids such as claviridenone-a (1),-b (2),-c (3),-d (4), and the 20-acetoxyl derivatives of 2 (5) and 3 (6) were isolated from C. viridis and their absolute stereostructures have been elucidated on the basis of chemical and physicochemical evidence including the application of the CD exciton chirality method. 2) A new trinorsesquiterpene named clavukerin A (32), which is a fairly unstable oil, was isolated from C. koellikeri and the absolute stereostructure has been determined by means of the chemical reactions, the CD analysis, and the X-ray crystallographic analysis of the diepoxide of clavukerin A (32).
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井本 昌宏, 島本 哲男, 山本 道治, 吉村 寛幸, 楠本 正一, 芝 哲夫, 直木 秀夫, 岩下 孝
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The lipophilic portion of bacterial lipopolysaccharide(LPS) is designated lipid A which is known to be responsible for most of the endotoxic activities of LPS. In the course of our synthetic study, we found that synthetic acyl disaccharide phosphates (4) corresponding to the proposed structure of lipid A showed certainly some of its typical biological activities. However, their potencies were significantly lower than those of natural samples. This prompted us to reinvestigate the chemical structure of natural lipid A. Thus, a homogeneous main component of E. coli, Re lipid A was isolated after chemical modification and its structure was elucidated as shown in 1 by combination of chemical method and the 2D-NMR technique. This was the first exact evidence for the acylation positions of the disaccharide backbone in the natural lipid A. The hitherto accepted structure (3) must be now revised. Synthesis of an acyl disaccharide diphosphate (2) based on our new structure is also being investigated.
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八木沢 尚正, 嶋田 信義, 長縄 博, 滝田 智久, 梅沢 浜夫, 中村 光, 飯高 洋一, 加藤 国基, 藤井 昭男
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Oxanosine is a novel nucleoside antibiotic produced by Streptomyces capreolus MG265-CF3. It is not only active against Escherichia coli K-12, Shigella sp. and Proteus sp. in peptone medium, but also inhibits the growth of leukemia L-1210 cells and prolongs the life span of tumor bearing mice. Recently, it has been noticed that formation of suppressor cells is suppressed and activity of macrophage is stimulated by oxanosine. The structure of oxanosine was elucidated to be 5-Amino-3-β-D-ribofuranosyl-3H-imidazo [4,5-d][1,3] oxazin-7-one by physicochemical data and X-ray crystallography. On the basis of chemical interconversion (scheme 1), the synthesis of oxanosine was achieved from readily available compound 4 via 5 steps. Synthesis and biological activities of 2'-deoxyoxanosine, which is derived from oxanosine, are also reported.
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畑中 顯和, 梶原 忠彦, 関谷 次郎
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Leaf alcohol (cis-3-hexenol) and leaf aldehyde (trans-2-hexenal), which are formed from cis-3-hexenal, are widely distributed in fresh leaves, vegetables and fruits and are responsible for "green odour" characteristic of leaves. We have demonstrated that the "green odour" (C_6-alcohols and -aldehydes) are biosynthesized by the enzymatic oxygenation (E'_2) and subsequent cleavage reaction (E"_2) from linolenic acid, which are liberated from phospholipid and neutral fats by acylhydlase in chloroplasts. In this paper, we describe the stereochemistry, the substrate specificity, the reaction mechanism and plant physiological regulation factor in enzymatic oxygenative-cleavage reaction. 1) The enantiomeric composition of the hydroperoxide produced by E'_2 was determined by GLC and the regiospecific and geometrical compositions were determined by HPLC. In the enzymatic cleavage reaction of 13-hydroperoxide to C_6-aldehyde, this compound was produced from L-form of hydroperoxide enantioselectively. 2) The isotope effect was observed in the E"_2 reaction by enzymes such as tea leaves, tea chloroplast and watermelon seedling. 3) The oxygenative activities have related to temperature and solar radiation and cleavage reaction activities have the correlation with the chlorophyll content of green leaves.
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妹尾 修次郎, 魚森 温子, 高山 陽子, 武田 健一
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^<13>C signals of C-26 (pro-R methyl group at C-25) and C-27 (pro-S) of sitosteryl acetate and its 24β epimer, clionasteryl acetate, which were chemically derived from ^<13>C-enriched isofucosteryl acetate (3-II), were assigned using the 'INADEQUATE' ^<13>C-NMR method. 3-II was obtained from the cell cultures of Physalis peruviana grown in the presence of [1,2-^<13>C]AcONa, followed by acetylation. As C-26 of 3-II is known to be derived from C-2 of mevalonate (MVA), the signals at δ 20.93 and δ 21.01 of 3-II could be assigned to C-26 and C-27, respectively. 3-II was then converted into a mixture of [^<13>C, 24-^2H, 28-^2H]sitosteryl acetate (10) and [^<13>C, 24-^2H, 28-^2H]clionasteryl acetate (11) by the catalytic deuteration. ^<13>C-^<13>C coupled signals due to C-27 of the respective 10 and 11 were observed selectively in the 'INADEQUATE' spectrum of the mixture. Thus the signals at δ 18.98 and δ 19.75 in 10 and the signals at δ 18.92 and δ 19.53 in 11 could be assigned to C-27 and C-26, respectively. The ^<13>-labelling patterns of C-26 and C-27 of several typical phytosterols, sitosterol (6), stigmasterol (8), α-spinasterol (12) and 24-methylene cholesterol (2), biosynthesized from [1,2-^<13>C]-AcONa in the cell cultures of Physalis peruviana, Bupleurum falcatum, Dioscorea tokoro, and Isodon japonicus were also examined. In all cases, C-26 (pro-R methyl group) originated predominantly from C-2 of MVA and C-27 from C-6 of MVA.
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小林 正紀, 佐上(高橋) 郁子, 伊藤 美智夫, 古山 種俊, 小倉 協三
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In order to study the stereochemical course of the C-C bond formation in the chain elongation of isoprenoid biosynthesis, we improved the Cornforth's method so that it could be applied more widely and directly to prenyltransferases. In contrast to the original method that requires chirally labelled deutero-mevalonic acids and an enzyme system containing several enzymes in addition to prenyltransferase, our method requires easily obtainable E- or z-4-deutero-isopentenyl pyrophosphate and prenyltransferase. The applicability was warranted by the observation that the chirally labelled 4,8-dideutero-farnesol derived in a good yield from E- or z-4-deutero-isopentenyl pyrophosphate by the reaction with dimethyl-allyl pyrophosphate and pig liver farnesyl pyrophosphate synthetase was converted by ozonolysis into S-(+) or R-(-)levulinic acid. We separated from Bacillus subtilis undecaprenyl pyrophosphate synthetase which catalyzed the cis condensation of isopentenyl pyrophosphate with elimination of the pro-S hydrogen at C-2. The configuration of the deutero-levulinic acid obtained by the new method is being determined.
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菅 隆幸, 平田 敏文, 青木 正, 岡村 真延, 大西 康裕, 片岡 俊哉, 皿谷 良夫
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In contrast to the Cornforth's basic principle for the isoprenoid biosynthesis, we have recently found that the unusual elimination of the pro-4S hydrogen of MVA took place in the formation of the Z-isoprene residue during the biosynthesis of polyprenols, named malloprenols, in Mallotus japonicus. We have now investigated (i) the enzyme system participating in the malloprenol biosynthesis, (ii) the stereochemistry of the hydrogen elimination in the formation of malloprenol with the enzyme system, and (iii) occurrence of the unusual hydrogen elimination in the other species of higher plants. The enzyme system participating in the biosynthesis of malloprenols was purified by fractionation with ammonium sulfate and a DEAE-cellulose column. The enzyme system was found to be different from the system which participates in the biosynthesis of farnesol. Occurrence of the unusual hydrogen elimination in the biosynthesis of the Z-isoprene chain of malloprenols was confirmed by incubating IPP-4-^<14>C, (2S)-2-^3H and its (2R)-2-^3H isomer with the enzyme system. On the other hand, occurrence of such an unusual hydrogen elimination was demonstrated by determination of the ^3H/^<14>C ratio in polyprenols biosynthesized from MVA-2-^<14>C, (4R)-4-^3H and its (4S)-4-^3H isomer with Aleurites cordata, Alnus serrulatoides, Aesculus turbinate, Betula platyphylla, Cleome spinosa, and Triadica sebifera. Consequently, it was suggested that elimination of the pro-4S hydrogen of MVA might be the usual mode in the formation of the Z-isoprene chain of polyprenols in higher plants.
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真部 俊一, 高柳 久男, 西野 親生
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Males of the American cockroache (Periplaneta americana) exhibit a typical sexual display against sex pheromones [periplanone-A (PA) and -B (PB)] and sex pheromone mimics [germacrene-D (GD), (+)-bornyl acetate (BA) and (+)-trans-verbenyl acetate (VA)], although the structures of the compounds are different each other. Therefore, we have interested in solving why the chemicals with different structures cause the same response of the males. As the first step, VA and its many analogs were subjected to elucidate important chemical factors in VA for sex pheromonal activity. Consequently, six items of the important factors were induced from the structure-activity investigation with the analogs. For examining the olfactory receptor systems for the sexually active compounds, the differential saturation electroantennogram (EAG) technique was employed. Monoterpenoid sex pheromone mimics were consequently concluded to participate in the sex pheromone receptors responsible for PB. According to the above EAG result, the structural overap between PB and VaP was carried out using a computer display considering the conformational energies of the compounds. The important factors in VaP could be reproduced in some moieties in PB (Fig. 4). This study involves a general methodological approach to the odor-receptor investigation.
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中崎 昌雄, 近松 啓明, 苗村 浩一郎, 廣瀬 良樹
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セッションID: 38
発行日: 1983/09/15
公開日: 2017/08/18
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The stereochemistry of HLADH-mediated oxidoreduction of C_1-ketones was governed by the same "quadrant rule" observed in the microbial reduction which states that hydrogen attack from the lower quadrants is most favored for the C_1-1 quadrant orientation. Two completely opposite stereospecificities toward C_2-ketones which were found in the microbial reduction and HLADH-catalyzed oxidoreduction have led us to propose the microbial P-C_2-ketone rule and the HLADH M-C_2-ketone rule. An extension of these studies has prompted us to examine the stereochemistry of the metabolites of the "meso diketones". The microbial reduction of 1,10-dioxo[2.2]metacyclophane (9) presented the first established example of the enantiotopic selectivity with respect to the plane of prochirality. HLADH-mediated reduction differentiated between the enantiotopic carbonyl groups in cis-decalin-2,7-dione (14) and its 10-methyl derivative 15 to provide (-)-(7S,9S,10R)-cis,cis-ketols 16 and 17 respectively by the re-face attack of hydrogen on the pro-R carbonyl group in the substrates. On the other hand, the microbial reduction showed an opposite selectivity to provide (-)-(7S,9R,10S)-cis,trans-ketols 18 and 19 respectively by the re-face attack of hydrogen on the pro-S carbonyl group. Both (-)-ketols 16 and 17 were converted via (+)-22 and 23 into respective (+)-twistane (24) and (+)-1-methyltwistane (25) of high optical purity.
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酒井 浄, 石黒 靖尚, 舟越 和久, 上野 貢嗣, 末宗 洋
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セッションID: 39
発行日: 1983/09/15
公開日: 2017/08/18
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Variously functionalized cyclopentanones are important as starting materials for the synthesis of natural products. We have succeeded in a simple, highly stereospecific synthesis of five membered ring ketone using Wilkinson complex. Thus, the precursors, 1-al-4-enes(4a-e,11,13) prepared in optically active form from D-limonene, (+)-limonen-10-ol and 1-carvone in three steps were submitted for RhCl(PPh_3)_3-catalyzed cyclization in CH_2Cl_2 to afford the cis-3,4-disubstituted cyclopentanones(14-22) in good yield (Table 2). The following results were obtained in this cyclization. 1) In all cases, the cis-3,4-disubstituted cyclopentanones were stereospecifically obtained as the sole products. 2) The cyclization reaction of the six membered lactols(12,13) was found to proceed very slowly even if at high temperature. 3) The cis-3,4-disubstituted cyclopentanones obtained in this method were also found to be applicable for the synthesis of bicyclic ketone(23). 4) The configurations of 3,4-disubstituents in each compounds were clarified by the way of chemical correlation and spectral analyses. Further application for the synthesis of ent-cis,cis-dihydro-nepetalactone(39) will be discussed.
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岩田 宙造, 中村 静夫, 篠尾 恭隆, 符阪 隆文, 岸本 みちえ, 上辻 秀和, 前崎 直容, 田中 徹明
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セッションID: 40
発行日: 1983/09/15
公開日: 2017/08/18
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Stereochemistry of the spirodienone esters 7a and 7b obtained by the intramolecular cyclization of phenolic bromo ester 9 was established by ^<13>C-NMR spectral analysis and chemical transformation to trans- and cis-1,4-dimethyltetralins 13a and 13b. It was proved that the cis-isomer 7b was the stable form. Compounds 7a and 7b were treated with a large excess of methyl lithium followed by a Lewis acid [SiO_2 for 7a and Mg(ClO_4)_2 for 7b] treatment to give tricyclic dienes 8a and 8b in 37 and 90% yields, respectively. The metal-ammonia reduction [Li (20 equiv.)/NH_3/THF/ t-BuOH/-40°] of 8a gave (±)-β-acorenol 2 in 81% yield. On the other hand, 8b afforded a mixture of 4-epi-β-acorenol 18 (10%), a disubstituted olefin 19 (66%) and a perhydro compound 20 (20%) under the same conditions. The yield of 18 was raised to 25% by altering the reaction conditions [Na (8 equiv.)/NH_3/THF/t-BuOH/-20°]. Dehydration (Al_2O_3/Py/200°) of 18 gave 4-epi-β-acoradiene 17 (78%), which was reduced with Li/EtNH_2 to give 16 (75%). (±)-Acorenone 5 was obtained by the allylic oxidation of 16 with SeO_2 in 70% yield.
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大塚 俊一, 早坂 和裕, 白浜 晴久, 松本 毅
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セッションID: 41
発行日: 1983/09/15
公開日: 2017/08/18
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1) Pentalenolactone (PL) H and G, and PL have been derived from humulene through biomimetic pathway. Comparison of NMR spectra of PL E, F, G, H and PL and their epimers suggested that stereochemistry of the epoxide moiety of PL-G and H were probably incorrect. 2) Dactylol (isolated from sea hare) has been derived from africanol which was previously synthesized from humulene by us. The former transformation has been accomplished through the cyclopropane sliding reaction as a key step, as shown in Scheme 3.
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富岡 清, 増見 史生, 山下 豊春, 古賀 憲司
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セッションID: 42
発行日: 1983/09/15
公開日: 2017/08/18
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The development of methodology for the asymmetric total synthesis of the biologically active natural products is an area of fruitful and challenging current research. We have reported a highly efficient enantioselective and diasteroselective synthesis of 1,2-disubstituted cycloalkanecarboxaldehydes based on the controlling of the substrate conformation by virtue of chelation. Herein we wish to report successful application of the method to the first asymmetric total synthesis of (+)-ivalin 1, a representative of the class of antitumor eudesmane sesquiterpene lactones. The reaction of isopropenyl Grignard reagent with a chiral α,β-unsaturated imine 22 has been shown to undergo a highly enantioselective 1,4-addition-alkylation sequence, giving 6 in 95% e.e. Then 6 was converted into 5. Ene-carbonyl cyclization of 5 with SnCl_4 afforded selectively 30 in 61% yield. By the reaction of the corresponding mesylate 33 with KO_2 in DMSO followed by protection the stereoinversion of the OH group in 30 was carried out to give 34. Alkylation of 34 with BrCH_2CO_2CH_3 and epimerization afforded 36. Subsequent construction of α-methylene lactone moiety has culminated in a first asymmetric total synthesis of the optically pure eudesmane sesquiterpene (+)-ivalin 1.
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柴崎 正勝, 間瀬 俊明, 池上 四郎
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セッションID: 43
発行日: 1983/09/15
公開日: 2017/08/18
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Studies directed toward the first total synthesis of Δ^<9(12)>-capnellene-3β, 8β, 10α-triol(3) is reported. In the first part of this presentation, development of a general synthetic route to the bisallylic alcohol functionality, which is uniquely associated with the capnellane alcohols(1〜6), is described. Transformation of the simple ketone(9) to the bisallylic alcohol(8), which involves the reaction of the epoxide(21) with trimethylsilyl-lithium in HMPA as a key step, proceeded quite nicely in ca. 16% overall yield. Cyclization of the β-keto ester(13), probably a mixture of the stereoisomers, afforded the stereochemically homogeneous tricycle(15) via base-induced epimerization. In the second, synthesis of the key intermediate(22) for Δ^<9(12)>-capnellene-3β, 8β, 10α-triol(3) is presented. Retrosynthetic analysis is based on cyclization of the allylsilane(25) to 34. Along this line, the key intermediate(22) has been obtained from 1,3-cyclohexadiene in a stereocontrolled manner. In the third, synthetic approach to Δ^<9(12)>_capnellene-3β, 8β, 10α-triol(3) is discussed. This approach involves the same synthetic sequence described above(9→8). Conversion of 22 to the tricycle(41,) has been already accomplished. Transformation of 41 to the natural product(3) is currently under investigation.
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角田 鉄人, 児玉 三明, 樺沢 靖弘, 伊東 〓
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セッションID: 44
発行日: 1983/09/15
公開日: 2017/08/18
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Synthetic effort toward two sesquiterpenes, silphinene (4) and senoxydene (5), and a diterpene, laurenene (6), is described. Since these compounds contain common structural feature, angular triquinane with very similar substitution pattern, we have formulated a synthetic strategy starting from the readily available dicyclopentadiene and branching off at certain points to culminate in the synthesis of all three, as is shown in Scheme I. Following reaction sequence shown in Scheme II and III, silphinene (4) was synthesized. Synthesis of senoxydene (5) branched off at synthetic intermediate 20 and, by the sequence shown in Scheme IV and V, a compound having the structure proposed by Bohlmann was achieved. However, PMR spectrum of the compound was not identical with the published data. There is a possibility that the natural product has a different structure. The synthesis of laurenene (6) was anticipated to be most difficult and therefore challenging, because of severe steric congestion. Although it has not yet been accomplished, the progress will be reported.
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