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小山 泰正, 深草 佑一, 興村 伸夫, 山岸 三郎, 新井 正
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Acetone extracts of the mycelial cake of Streptomyces luteoreticuli Arai yield a new toxic, nitro-containing metabolite (I), C_<19>H_<19>HO_5, m.p. 184.5-185°, which was named luteoreticulin. Oxidation of (I) with potassium permanganate gave p-nitrobenzoic acid, and with alkaline hydrogen peroxide gave an acid (III), C_<13>H_<13>NO_4. The ethyl ester of (III) was identified with ethyl 2,4- dimethyl-5-(p-nitrophenyl)-2,4-pentadienoate prepared from the synthetic pathway by means of mixed m.p., UV, IR, and NMR. On the hydrogenation over Adams catalyst, (I) absorbed five moles of hydrogen to give (II). The IR and UV spectra of (II) indicate the presence of a 4-methoxy-2-pyrone moiety in (I). Hydrolysis of (I) with barium hydroxide in 50%-ethanol gave a diketone (VIII), which establishes the relative position of the substituted groups on the 4-methoxy-2-pyrone. On the basis of NMR studios of (I), (IV) and related compounds, geometric configuration of (I) was deduced to be trans-trans configuration. The structure (I)_c including the geometric configuration was established for luteoreticulin.
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柴田 承二, 荻原 幸夫, 小林 信子, 妹尾 修次郎, 三川 潮, 飯高 洋一, 北川 勲
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The structures of some new bianthraquinones isolated from Penicillium islandicum Sopp were established as (IX〜XTV). The revised structures of rugulosin (XXI), luteoskyrin (XXII) and rubroskyrin (XXIII) are discussed mainly on the basis of the results of NMR spectral analysis (see Fig. I, II and III; Tab. I and II).
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水野 公明, 浅井 満子, 原田 節夫, 室井 正之, 貴志 豊和, 水田 栄治, 寺尾 泰次, 三木 卓一
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Tolypomycin Y (C_<43>H_<54>N_2O_<14>, I), which exhibits a strong inhibition against gram positive bacteria, was isolated from Streptomyces tolypophorus. Tolypomycin Y upon redaction with H_2/pt, resulted in tolypomycin R (II), which on oxidation gave I. Mild acid hydrolysis of I afforded an aminosugar, tolyposamine (C_6H_<13>NO_2, III) and a yellow quinone, tolypomycinone (C_<37>H_<43>NO_<13>, IV). III gave the N-benzoyl-O-methyl-derivatives (Va, Vb). The periodate oxidation of III gave acetaldehyde, while the permanganate oxidation led to succinic acid and ammonia. From these results, III is assumed to be 4-amino-2,3,4,6-tetradeoxypyranohexose. When IV was hydrolyzed with acid, a naphthoquinone, 2-amino-8,11-dihydroxy-7,12-dimethyl-11,12-dihydrofuro[3,2-f]-1,4-naphthoquinone-11-one (IX), tolypolide F_1 (C_<22>H_<30>O_7; XIV) and F_2 (XV) were obtained. A γ-lactone, tolypolide F_3 (XVII), was obtained by the oxidation of XIV with OsO_4 followed by Pb(OAc)_4 oxidation. Thus, IV contains a naphthoquinone (IX) and an open chain form of tolypolide F_1. Chemical properties and NMR spin decoupling studies of IV and methoxytolypocyclonone (XVIII) support the structure IV. By the treatment with conc. HCl in methanol, I afforded 1'-O-methyltolypocyclonide (XXII), which can be derived into Va, Vb and XVIII. All the proton signals in the NMR of I can reasonably be accounted for by the proton signals of III and IV. The NMR indicates also that III combines at the C_4 position of IV. On the basi of these findings the structure I is proposed for tolypomycin Y.
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田中 邦彦, 植田 育男, 刈米 和夫, 海尾 澄則
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Total synthesis of Pyrrolnitrin (I), an antibiotic from Pseudomonas pyrocinia, was achieved by several different routes. At first, a key intermediate (IIIa) was prepared by the introduction of a methyl group to the α-position of the pyrrole (Va), Paal Knorr condensation of the 2,5-hexanedione (XII) and the introduction of two methyl groups to the pyrrole (XIV). The second type of key intermediates, β-aryl-5-methyl-2-pyrrolecarboxylic esters (XXXI and II), were synthesized from pyrroles, XIV, XXIII and XX, mainly by the methylation or methoxycarbonylation to the α-position. And the third type of key intermediates, 3-aryl-2,5-pyrroledicarboxylic esters, XXVIa, b, d, were synthesized by the introduction of the ethoxycarbonyl group to the pyrrole (XX), and by the condensation of the arylglyoxals (XXIVb, d) with dimethyl acetyliminodiacetate (XXV). The α,α'-disubstituted-3-arylpyrroles, IIIa, XXI and XXVIa, thus prepared, were transformed to Pyrrolnitrin (I) by chlorination with SO_2Cl_2, hydrolysis and decayboxylation. It was also found that 3-arylpyrrolecarboxylic esters, XLI, XLV, XXXIXa, XLVII and XLVI, were transformed directly to I by the treatment with conc. H_2SO_4. And in the course of the synthetic research, a new method of pyrrole ringclosure was developed: nitro-chlorophenylpyruvates (VIIIa and XVIII) and the nitro-chlorophenylacetone (Xa) were condensed with aminoacetal (XIII) to give pyrroles, XIV, XX and XXIII. And Hantzsch reaction was extended also to give the pyrrole (XIV).
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佐伯 博道, 大木 英二
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Some 6-azido-5-tosyloxy-hexofuranoses were treated with lithium aluminum hydride or with sodium borohydride/cobalt(II)tris-(α,α'-dipyridyl)bromide to yield the corresponding 5,6-epimines. Thus, 3-O-benzyl-5,6-dideoxy-5,6-epimino-1,2-O-isopropylidene-β-L-idofuranose (10), -α-D-glucofuranose (16), 5,6-dideoxy-5,6-epimino-1,2-O-isopropylidene-β-L-idofuranose (21), and methyl 2,3-di-O-benzyl-5,6-dideoxy-5,6-epimino-α-L-altrofuranoside (32) were synthesized and characterized as their acetates. It was also found that the hydroxyl function in the 3-position considerably affected formation of aziridine or displacement of 5-O-tosyloxy group. The N-acetates of these 5,6-epimines were unstable to acids and treatment with acetic acid easily afforded 6-acetoxy-5-acetamido-hexofuranoses under an attack of acetate ion in the terminal position. Thus, 17 was converted into 6-O-acetyl-5-acetamido-3-O-benzyl-5-deoxy-1,2-O-isopropylidene-α-D-glucofuranose (39), which gave 5-amino-5-deoxy-1,2-O-isopropylidene-α-D-glucofuranose (40) on debenzylation and hydrolysis. Successive treatment of 40 by N- and O-trifluoroacetylation, followed by de-O-acetonation with acids and removal of the protecting group with bases resulted in its conversion, in a good yield, into Nojirimycin (1), a monosaccharide antibiotic produced by some strains of Streptomyces which is active against Sarcina lutea and Xanthomonas oryzae.
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須原 康次, 佐々木 藤紀, 前田 謙二, 梅沢 浜夫, 大野 雅二
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The stereoselective total synthesis of kasugamycin has been completed. 6-Methyl-3,4-dihydro-2H-pyran-2-one (II) was treated with NOCl to give III, which was hydrolyzed to give IV. The catalytic reduction of IV afforded stereoselectively erythro isomer (V), which was lactonized by treatment with Ac_2O, affording VI. The lactone VI was reduced with LiAlH_4 to a hemiacetal (VII), which by treatment with Ac_2O-Py gave VIIIa and VIIIb. The compound (VIIIb) was treated with NOCl to afford the expected chloronitroso dimer (XI). Displacement with lower alcohols such as CH_3OH, EtOH and i-PrOH afforded the corresponding α-glycosides of (XIIa), (XIIb) and (XIIc), respectively. The compound (XIIa) was reduced with hydrogen over Pt, giving XIIIa which gave dl-methylkasugaminide (XIIIc) by subsequent hydrolysis with Ba(OH)_2. Thus, the synthesis of the deoxy-amino sugar moiety of kasugamycin has been accomplished by stereoselective reactions. The compound (XI) was treated with excess of 1:2,3:4-di-O-isopropylidene-d-inositol followed by hydrogenation and hydrolysis. The reaction product was purified by chromatography using Amberlite CG-50 and by recrystallization, affording XIIIb. The synthetic material (XIIIb) was confirmed to be identical with N-acetyl derivative of natural kasuganobiosamine in all respects. Kasuganobiosamine (XIIId) was obtained by further hydrolysis. The synthesis of XIIId completes the total synthesis of kasugamycin, since kasuganobiosamine was previously converted to kasugamycin (I) by treatment with diethyl ester of oxaldiimidic acid and mild hydrolysis with HCl in our structural studies.
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原田 宣之, 中西 香爾, 大橋 元明
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Brewster's benzoate rule is widely employed to determine the absolute configuration of cyclic sec-alcohols, but is not applicable to certain types of compounds, e. g., those in which the carbinyl carbon is flanked by two methylene groups (No. 4 in Table 1), and those in which one of the carbons adjacent to the carbinyl carbon is the bulkier and also the more polar (Fig. 3). I. The Benzoate Sector Rule We have found that the strong Cotton effect of benzoates due to π-π^* intramolecular charge transfer transition at ca 225mμ permits one to predict the absolute configurations of various cyclic sec-hydroxyl groups including those mentioned above. The sectors are set up as shown in Fig. 1. The preferred conformation of the benzoyloxy group is assumed to be the one in which it lies staggered between the carbinyl hydrogen and the smaller substituent. The benzoate is viewed from the para-position and the rotatory contribution of α,β- and β,γ-bonds are considered. The bonds falling in the shaded sectors in Fig. 1 make a positive contribution to the sign of the 230mμ Cotton effect. The contribution of a double bond would be larger than that of a single bond because of the larger polarizability. Pertinent examples of the application of the benzoate sector rule, mainly from the steroid field, are listed in Table 1. This sector rule is corroborated by simple LCAO MO calculations. II. Optical Rotatory Power of the Benzoate Group The fact that the benzoate Cotton effect was assigned to the π-π^* intramolecular charge transfer transition was ascertained by observing the red shift caused by para-substituents. (Table 2). This is of practical value since the benzoate absorption can be shifted to longer wavelengths when results are ambiguous because of overlap of the benzoate and substrate absorptions (No. 15, Table 1). III. Optical Rotation of α-glycol dibenzoates Dibenzoates show two Cotton effects of opposite sign centered at 225mμ, in which the sign located at the longer wavelength depends on the chilarity of the glycol. (Table 3).
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佐々木 慎一, 阿部 英次, 工藤 喜弘, 落合 周吉, 坂本 正義, 入江田 紀夫, 石田 嘉明
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An actual attempt to feed physical data, acquired via computers from MS, NMR, IR and UV, into a central computer which is programmed to structure elucidation based on a combination of all four types of data is being carried out. In this paper, the roll of each computer connected to the spectrometer (Figs. 1, 2, 3 and 4) and the program resident on each of them are explained in detail (Table 1, Figs. 5 and 6). For instance, the computer connected to the NMR spectrometer records all signals and determines chemical shifts and coupling constants by the order of the program specially made by authors (figs. 2 and 3). The data computed by the method gave the appropriate molecular formulae and partial structures for several kinds of aliphatic and aromatic compounds (Figs. 7, 8, 9 and 10).
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富田 真雄, 新宮 徹朗, 古川 宏, 照井 彬弘
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The conformations of some macro-ring compounds have recently been studied to report important conclusions that such a ring is fixed in one conformation in spite of their considerable flexibility indicated by examinations of molecular models. From such a point of view, a series of biscoclaurine type compounds are very interesting to investigate their conformations. The chemical structure and configuration of isotrilobine (I) were already elucidated: it possesses 18-membered macro-ring consisting of bisbenzylisoquinoline bonded by ether linkage. Isotrilobine was selected as the first example in our conformational studies of biscoclaurine type compounds, because it is assumed to be rather inflexible than the others. Proton magnetic multiple resonance spectra at 100MHz of isotrilobine in a pyridine-d_5 solution have been examined to reveal its possible conformation mainly by studying their spin-decoupling features and so-called intramolecular nuclear Overhauser effects developed recently.
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坂井 進一郎, 久保 陽徳, 浜本 武紀, 若林 幹夫, 高橋 勝弘, 大谷 裕之, 萩庭 丈寿
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Recently, we isolated four new indolic alkaloids-Gardneramine, Gardnerine(I), Gardnutine(II) and Hydroxygardnutine(III)-from Gardneria nutans Sieb. et Zucc. (Loganiaceae) and elucidated structures of (I), (II), (III) on the basis of chemical correlation with each other. Now, in order to clarify the absolute configuration of Gardnerine(I), attempts to interrelate Gardnerine(I) to Ajmaline, whose absolute configuration was already established, were accomplished successfully in two different routes-namely A and B route respectively. Gardnerine(I) and Ajmaline afford (X) under the A route which was shown in the chart 4 and 5. On the other hand, Gardnerine(I) and Isoajmaline afford (XXII) under the B route which was shown in the chart 6 and 7. Thus the structure and the absolute configuration of Gardnerine (I) was established with the exception of the geometry of the ethylidene group.
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正宗 直, 村井 章夫, 折登 一彦, 佐藤 紀朗, 西村 健, 杉野目 浩
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Dihydrojervine (2) has been reported to possess α-hydrogens at both C-12 and C-13 on the basis of the chemical behavior of its degradation product 4, whose configuration has been assigned as α-H at the carbons. The present paper describes that the configuration should be revised as shown by formula 2. Compound 6b, obtained by hydrogenation of 4b, gave its deoxo derivative (9a) by the Wolff-Kishner reaction. A series of reactions summarized in Charts 2, 3 and 4 indicates that these compounds have to be formulated as 9 and 6. These revised formulae lead to revision of configuration assigned for other degradation products 5, 7 and 8. On the other hand, compounds 26 and 10, which are formed by the Birch reduction of 11-deoxojervine (28) and jervine (1), respectively, and have a double bond at C-13-C-17, have been confirmed to be cis-fused at C/D linkage by a series of reactions shown in Charts 5 and 6. ORD curves and NMR spectra of a number of these and other compounds derived from 1 were measured and parts of the results are summarized in Tables 1 and 2. In view of the spectral data of these compounds and 2, coupling constants between hydrogens at C-12 and C-13 of compounds 41 and 42 derived from 2 as well as the chemical behavior of 2 (Charts 1 and 7), it is concluded that dihydrojervine should be formulated as 2 (trans-fused C/D linkage). In addition, on the basis of these revised assignments, anomalous behavior in the hydrogenation of 1 and its various derivatives is satisfactorily explained.
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岡本 敏彦, 鳥井 良彦, 磯谷 謡
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Methanol extract of the bulbs of Lycoris radiata Herb. has strong growth-inhibiting actions on Avena straight growth test and rice seedling test. The methanol extract was purified and two plant growth inhibitors, lycoricidinol and lycoricidine, were isolated. In this paper we wish to report the establishment of the structures. Lycoricidinol, C_<14>H_<13>O_7N, has a cheleted phenolic hydroxy group, a methylenedioxy group, a tri-substituted double bond conjugated with an aromatic ring system, three vicinal hydroxy groups and an amidic group. Lycoricidine, C_<14>H_<13>O_6N, has same functional groups as lycorici dinol without a phenolic hydroxy group. When lycoricidine and lycoricidinol are treated with methanolic hydrochloric acid, arolycoricidine and arolycoricidinol are respectively obtained, eliminating two molecules of water. And arolycoricidine derivative is identical with the authentic sample obtained from Pschorr cyclization of 12 in IR spectrum, TLC and mixed melting point. Thus the structure of arolycoricidine was definitely established. To satisly the above deta, the structures of lycoricidine and lycoricidinol must be expressed by the formulae 2 and 1, respectively.
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入川 肇, 桜井 寛, 戸田 正明, 山村 庄亮, 平田 義正
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An alkaloid of Daphniphyllum macropodum Miquel was first isolated in 1909 as a white amorphous powder, m.p. 75-84°, C_<27>H_<41>O_4N, and named dephnimacrine. We have examined the alkaloidal components of the same plant and isolated nine new alkaloids. The structures of the two typical alkaloids, daphniphylline (I) and yuzurimine (X), were determined by X-ray diffraction studies and the structures of other alkaloids, codaphniphylline (VIII), yuzurimine A (XI), yuzurimine B (XII) and secodaphniphylline (XIV), were deduced by the chemical reactions and the careful comparison of physical data among them. These natural products are regarded as a new type of alkaloid.
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三島 洋, 小木曽 彰, 高橋 秀次, 倉林 正明
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Piper futokadzura Zieb. et Zucc. (Piperaceae) is a common plant growing in the pacific coast of southern Japan, the leaves and stem of which are used as an indigenous medicine. As principles for the fragrant odor of this plant, α-pinene, camphene, β-pinene, sabinene, limonene and isoasarone were detected by means of fractional distillation and gas chromatography. Investigation of the ether extract of the leaves and stem led to the isolation of four new crystalline components designated as futoxide, C_<18>H_<18>O_8, m,p, 151-3°, futoenone, C_<20>H_<20>O_<5>, m.p. 197°, futoquinol, C_<21>H_<22>O_5, m.p. 97-8°and futoamide, C_<18>H_<23>O3N, m.p. 128-130°, besides β-sitosterol and stigmasterol. Futoxide was obtained in the highest yield of these components. These structures were determined by chemico-physical methods. Recently Kupchan et al isolated crotepoxide, having significant tumor inhibitory activity, from alcoholic extracts of the fruits of Croton macrostachys Hochst. ex A. Rich; (Euphorbiaceae). They elucidated the structure of crotepoxide by X-ray analysis. Comparison of futoxide with a sample of crotepoxide (by mixed m.p., mixed TLC, and IR spectral comparison) showed that the materials are identical.
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西尾 健司, 藤原 隆二, 冨田 研一, 石井 永, 犬伏 康夫, 原山 尚
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Serratinine, which is a new alkaloid isolated by Inubushi et al. in 1962, has essentially an unique backbone structure other than any Lycopodium alkaloid which had been found so far. Its chemical structure was already determined and its absolute structure was also suggested by Inubushi et al., while the present authors tried to confirm this structure by X-ray method. Using a single crystal of the serratinine derivative, 13-acetyl-8-p-bromobenzoyl serratinine, for the X-rays, we measured the intensities by the photographic method with Cu-Ka radiation, and tried to determine the absolute structure by the Bijvoet's method. The crystallographic data are: monoclinic, a=12.47A, b=11.44A, c=17.52A and B=104°15', observed density, ρ0=1.38g/cc., the number of molecules per unit cell, Z=4, and space group C2. The structure determination was carried out by heavy atom method using 968 reflections from b-axis Weissenberg photographs. After several cycles of the block diagonal least squares refinement, the reliability factor, R, was dropped to 10%. The stereostructure thus established is either (V) or its mirror image, (VI), and comparing this with the structure (I) which was determined chemically, it was clearly shown that the former is different from the latter in the stereochemical configuration around C4: the spatial relation between C_4-N bond and C_<12>-C_<13> bond in either (V) or (VI) is trans form to the B ring, while the relation in (I) is cis form as shown in Pig. 4. The obtained bond lengths and bond angles are all acceptable values, and the absolute structure determination of this compound is now in progress.
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松川 貞央, 山口 正雄
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The authors have reported previously that a fluoresoent compound, tentatively named as f_2' was isolated from the urine of patients with rheumatoid arthritis specifically and its structure was elucidated to be pyrrole-1,2-dicarboimide (2) on the basis of its chemical and physical properties. This report deals with the synthesis of (2) from both pyrroles and L-proline. Carbonyl group was easily introduced at ring nitrogen of methyl pyrrole-2-carboxylate (4) by treating with potassium alkoxide and then ethyl chlorocarbonate or a large excess of phosgene in toluene giving diester (5) or di-N-pyrryl ketone (8), respectively, but they faced to several difficulties in the case of pyrrole-2-carbamide (10). While ammonolysis of the diester (5) or of the ketone (8) resulted bond cleavage between ring nitrogen and carbonyl group, however, preliminary experiment with the amide (10) and acetyl chloride revealed that pyridine was the best solvent and catalyst, and pyrolysis of the resultant ester-amide (13a) brought about ring closure to form the target imide (2) being identified with f_2'. Dehydrogenation of L-proline hydantoin (16) with paradium charcol in p-cymene at reflux afforded the pyrrole compound (2) in poor yield, too.
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目 武雄, 磯江 幸彦, 玄 亟培, 市川 博, 勝村 成雄, 植田 泰次
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In previous paper we reported the structure of actinidiolide(I) dihydroactinidiolide(II) and actinidol(III), the odd terpenes from Actinidia polygama Mig.. Recently, much attention has been devoted to dihydroactinidiolide because of its isolation from several species of plants as the principle of tea flavor. We herein report the simple synthetic route to dihydroactinidiolide, the biogenetic type synthesis of dihydroactinidiolide, actinidiolide and actinidol and the formation of allenic compound (VII) from β-ionol by photosensitized oxidation. The significance of photosensitized oxidation in the biogenesis of C-11 and C-13 terpenes was demonstrated.
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石井 宏, 東条 武彦, 湊 均
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Three closely related sesquiterpenes, liguloxide, liguloxidol and liguloxidol acetate, were isolated from the aerial part of Ligularia Fischeri Turcz. On the basis of spectral evidences and chemical transformations, such as dehydrogenation of liguloxide to S-guaiazulene and conversion of liguloxidol to a keto-acid 9, the plane structures 1, 2 and 3 were assigned to liguloxide, liguloxidol and liguloxidol acetate, respectively. The stereoformulae 12, 13 and 14 were given to these three compounds from the following observations: (a) BF_3 treatment of 10-epiliguloxide gave (+)-guaiol. (b) The i.r. spectrum of liguloxidol taken in dilute solution showed the presence of strong intramolecular hydrogen bonding (v_<max>. 3472cm.^<-1>). (c) o.r.d. determination of a ketone 4 showed a negative Cotton effect curve(a=-76). (d) LAH reduction of the ketone 4 predominantly produced liguloxidol. However, these assignments have proved to be incorrect in connection with structure elucidation of guaioxide: we have recently confirmed the absolute configuration of guaioxide, a constituent of guaiac wood oil, to be represented by the formula 16, and have found that 4-epiguaioxide 34 corresponds to liguloxide. According to this finding and the observation (b), the structures of liguloxidol and its acetate should be revised to 36 and 37 respectively. The observation (a) is compatible with the new structure 35 for 10-epiliguloxide, because it becomes reasonable to consider that there had occurred inversion of the configuration at C-7 during the transformation of this compound to (+)-guaiol. The other observations (c) and (d) also explain satisfactorily all the revised structures.
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和田 弘次郎, 榎本 祐司, 宗像 桂
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Three insect antifeedants, shiromodiol-diacetate, shiromodiol-monoacete and shiromool were isolated from the leaves of Parabenzoin trilobum Nakai. This report presents evidence which let us assign the absolute configuration (I) for shiromodiol-diacetate. On alkaline hydrolysis I, C_<19>H_<30>O_5 gave shiromodiol (II), C_<15>H_<26>O_3. Hydrogenation of II gave tetrahydro derivative (III). The comparison of the nmr of I and IV shows the presence of the partial structures (CH_3-C=CH, CH_3-C-O-CH) in I. On this basis, I has to be a monocarbocyclic compound. The spectral data of the oxidized products (V, VI, VII) suggest the presence of the partial structures, CH=C(CH_3)-CH_2-CH(OAc)- and CH_3-C-O-CH-CH(OAc)-CH in I. Moreover, dehydrogenation of I with Pd/C gave a 1.4.7-substituted azulene. This indicates that I has germacrane skeleton. Ozonolysis of I followed by the acid treatment, NaOH-AgNO_3 oxidation and NaIO_4 oxidation gave levulinic acid. Thus, the structure (I) was reasonably assigned to shiromodiol-diacetate. The relative configuration of I was assigned by the detailed analysis of the nmr spectrum of XI. The absolute configuration of I was finally established from the ORD of β,γ-unsaturated chromophore in V and VI.
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松本 毅, 白浜 晴久, 市原 耿民, 申 鉉渉, 香川 昌平, 目 不二雄, 宮野 勝次
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Total synthsis of illudin S was attempted according to the same procedure of that of illudin M. Stereoisomeric mixture 17, 18 which might serve as useful intermediates for the synthesis was prepared from 12 through several steps. Gas chromatographic separation of the mixture gave 17 and 18 in a ratio of 1:3. The stereochemistry of 17 was determined by correlation of its derivative 22 with an acetate of 26(trans). Preliminary attempts of the synthesis were made starting from stereoisomeric mixture 17, 18. Thus, Michael addition of 3 and the mixture gave a mixture of adducts 27. Pummerer reaction of 27 in acetic anhydride-pyridine proceeded slowly to give rearranged product 28 in low yield, though the same reaction in bromoacetic anhydride afforded a complicated mixture. Transketalization of 28 to 31 failed. However methoxy-acetate 30 which was obtained by Pummerer reaction of 27 in methoxy-acetic anhydride was smoothly converted to 31. Intramolecular aldol condensation of 31 with potassium tert-butoxide yielded an enone 32. Total synthesis of illudin S from 32 as well as separated isomers 17, 18 is in progress.
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中崎 昌雄, 苗村 浩一郎
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Optically active 3-oxo-8β(H),11α(H)-eudesm-4-en-8,13-olide(20) the racemic modification of which was a key compound in our total synthesis of (±)-artemisin(1) can be expected to become a relay compound linking natural (-)-artemisin and our optically inactive synthetic intermediates. Sodium borohydride reduction of (+)-isoalantolactone(2) afforded (+)-dihydroisoalantolactone(3) whose cis lactone ring could be transformed into the trans form by the following series of conversions. Alkaline hydrolysis opened the lactone ring yielding the hydroxy-acid which was immediately esterified with diazomethane to give the hydroxy-ester(6). Chromic anhydride oxidation in acetone followed by hydrolysis afforded the keto-acid(8). Thermodynamically controlled reduction with sodium in isopropyl alcohol gave the unsaturated acid(10) with 8α-hydroxyl group (equatorial). Lactonization could be achieved by heating in vacuo, and the resulting trans lactone (12) was refluxed in acetic acid with p-toluenesulfonic acid to give the unsaturated trans lactone with endo-cyclic double bond which could be also obtained directly from the hydroxy-acid(10) by refluxing in acetic acid with p-toluenesulfonic acid. Selenium dioxide oxidation in ethanol converted the lactone(13) into the requisite optically active key compound(20), m.p. 140-141°[α]_D+15.5°which was proved identical with the (+)-3-oxo-8β(H),11α(H)-eudesm-4-en-8,13-olide derived from (-)-artemisin. Identity was further confirmed by the comparison with our synthetic racemic compound. By the series of transformations which we had explored in the successful synthesis of (±)-artemisin, this α,β-unsaturated ketone was converted into natural (-)-artemisin.
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堀井 善一, 大川 和夫, 金 相元, 辻内 源英, 百瀬 雄章
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The structures of diphyllin (4), justicidin A (5) and taiwanin E (6) were found to be incorrect and to have to be revised to structures (1), (2) and (3), respectively, from the chemical and NMR spectral evidences. The benzhydrylsuccinic acid (20) was synthesized and converted, by a 8-step procedure as shown in Chart 1, to the Murakami-diphyllin (9). The selective cyclization of (20) gave cis- and trans-4-(3-bromo-4,5-dimethoxyphenyl)tetralone (28a,b: R=H) as expected, while the cyclization of debromo derivative (19) of (20) gave predominantly a trans-4-(3,4-methylenedioxyphenyl)tetralone (38), which was converted to a 1-hydroxy-2,3-naphthalide (4) by a similar 6-step procedure to (9) as shown in Chart 2. Compound (9) or (4) was found not to be identical with diphyllin. Consideration of the NMR spectra of aromatized 2,3-naphthalide lignans in which the 4-phenyl ring lies perpendicularly to the naphthalene ring and shields the lactone methylene in 1-hydroxy-2,3-naphthalide system (A) afforded an effective method to distinguish between systems (A) and (B) as shown in Table III. The lactone methylene of diphyllin, justicidin A or taiwanin E is obviously not shielded. The syntheses of them were achieved by the procedure shown in Chart 3, and followed by identification with natural samples. All the hitherto known aromatized α-hydroxy-2,3-naphthalide lignans, such as diphyllin, justicidin A, taiwanin E and dehydropodophyllotoxin, are now concluded to have 4-hydroxy-2,3-naphthalide system (B).
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釜野 徳明, 山本 博, 田中 義啓, 畑山 勝男, 篠原 道子, 小松 曼耆
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Among some twenty bufadienolides hitherto known, thirteen of them were isolated from the Chinese toad venom drug, Ch'an Su. We have recently described on the detection of unknown compounds with the isolation and characterization of them. The chloroform extract of Ch'an Su afforded a mixture of unknown materials by column chromatography on silica gel which was eluted by adopting the dry method using an n-hexane acetone mixture. By rechromatography of the mixture, there were obtained six bufadienolides, one of which was identified to be marinobufagin V, first isolation from Ch'an Su. The second compound, mp. 210-212°, was named resibufagin. This new bufadienolide was assigned the structure I (3β-hydroxy-19-oxo-14,15β-epoxy-5β-bufa-20,22-dienolide). The other four compounds was characterizated to be Bufogenin 3-hemisuberates. So, this new bufogenin esters have been elucidated to be cinobufagin 3-hemisuberate(IX), resibufogenin 3-hemisuberate(XII), bufalin 3-hemisuberate (XV) and gamabufotalin 3-hemisuberate(XVII)respectively. Our results, which demonstrated the occurrence of 3-(hydrogen suberoyl)-bufogenins, might be extended to the so-called "bufotoxins" to have suberoyl-arginine grouping at 3-position.
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清水 讓, 佐藤 好正, 三橋 博
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The structures of four new non-cardiac steroidal aglycones: ester A, fukujusone, adonilide and fukujusonorone, which had been isolated from the root of Adonis amurensis besides five other known substances, were discussed. Ester A is a nitrogen containing compound and was proved to be 12-O-nicotinoylisolineolon (IV). Fukujusone was given the structure of 3β,8β,14β-trihydroxy-5-pregnen-20-one (V) on chemical and physical basis. Adonilide is a γ-lactone and was assigned the structure of 14β,20α-epoxy-20β-hydroxy-18-oic acid lactone (IX). Fukujusonorone seems to be the first example of a genuine natural 18-norsteroid and was given the structure of 3β-hydroxy-18-norpregna-5,13(14)-dien-12,20-dione (XII). A sequence including β-keto acid decarboxylation was suggested as a possible mechanism of fukujusonorone biosynthesis, and its appliance in the chemical preparation of 18-norpregnanes was also stated.
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竹本 常松, 曳野 靖子, 在原 重信, 荒井 富雄, 奥山 徹, ヒキノ ヒロシ
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The first isolations of ecdysterone, inokosterone, and ponaster-ones from plants have led us to perform a wide screening of ecdysterols in vegetable sources by means of the Sarcophaga assay. As a result, it has been found that active substances are widely distributed in the plant kingdom and, in particular, frequently contained in ferns. Detailed survey of the ferns whose crude extracts exhibit moulting hormone activity has resulted in the isolations of new phytoecdysones, pterosterone, lemmasterone, shidasterone, and ponasteroside A, as well as the known ecdysterols, ecdysone, ponasterone A, and ecdysterone. On the basis of the chemical and physico-chemical evidence, pteroster-one, lemmasterone, shidasterone, and ponasteroside A have been concluded to have structures IV, V, VI, and VII, respectively.
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今井 俊司, 豊里 友良, 堀 正剛, 村田 栄子, 坂井 道彦, 中西 香爾
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A systematic screening of plants carefully selected to represent 186 families indigenous to Japan has been carried out and the screening of 1056 species has led to the discovery of several new plants as sources for the phytoecdysones. The crude extracts of plants were subjected to the newly developed Chilo dipping method for rapid assay of activity; the method has the advantage of being simple to manipulate, rapid, and highly sensitive. A separation technique employing automatic liquid chromatography on an Amberlite XAD-2 column has been found to be effective for separating and identifying the various phytoecdysones (Fig. 1). Extraction of the dry leaves (1.2 tons) of Podocarpus macrophyllus D.DON has resulted in the isolation of ecdysterone (2), ponasterone A (4), and four new ecdysones, makisterone A, B, C and D. Structural studies of the four new compounds based on spectroscopic data of the free and acetylated compounds has enabled one to assign structures 11, 12, 13 and 14, respectively, to makisterone A, B, C and D; it is interesting that a single plant has afforded a total of six active compounds ranging from C_<27> to C_<29>. Extraction of Ajuga incisa MAXIM. has given ecdysterone (2), cyasterone (16) and two additional compounds, ajugasterone A and B. The structure of ajugasterone B can be represented by (15), i.e., the first ecdysone containing an unsaturated side-chain.
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森 弘, 柴田 健雄, 常田 清, 沢井 政信
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Klyne and Stokes reported that the hydroxyl group at C-22 in natural 22-hydroxycholesterol (26) is α_F-oriented. In connection with studies on the synthesis of ecdysone in our laboratory, it was found that this assignment should be reversed. Lactone A (3) and B (4) were prepared from stigmasterol (1) by eight steps of reactions as key, intermediates for the synthesis of ecdysone and its isomer at C-22 (41). These lactones were introduced into diol A (5) and B (6), respectively, which were also synthesized from stigmasterol by another route. 5α-Cholestane-3β,22-diol (15a), in which the configuration at C-22 is apparently different from that of natural 22-hydroxycholesterol, was obtained by transformations from diol A (5). (Chart 2) The similar treatment of diol B (6) afforded 5α-cholestane-3β,22-diol (25b) identical with the hydrogenation product of natural 22-hydroxycholesterol. (Chart 3) On the other hand, 22-isoecdysone (41) was synthesized from lactone A (3) (Chart 4), and ecdysone from lactone B (4). Thus, the configuration of the 22-hydroxyl group in natural 22-hydroxycholesterol is the same as that of ecdysone. If the configuration assigned in ecdysone is considered to be unequivocal, natural 22-hydroxycholesterol must be formulated as 5-cholestene-3β,22β_F-diol.
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Herche Smith
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尾中 忠正
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Syntheses of two simple alkaloids of unique structures are described in two separate sections(I and II) I Synthesis of Shihunine(1) Two-step synthesis of shihunine has been achieved. The first step of the synthesis was Claisen condenzation of dimethylphthalate (4) with N-methylpyrrolidone(3) affording 3-(1-methyl-2-oxo-3-pyrrolidinylidene)phthalide(10). Then the ketonic fission of (10) gave shihunine(1), which was identical with the natural alkaloid in all respects. II Synthesis of Withasomnine(17) Three-step biogenetic-type synthesis of withasomnine(17) has been achieved. The first step of the synthesis was alkaline condenzation of benzylcyanide(25) with O-methylpyrrolidone(26), affording 1-(2-pyrrolidinylidene)-1-phenylacetonitril(27). The condenzation product(27) was reduced to assumed biosynthetic intermediate diamine(24), which was, then, cyclized to natural withasomnine(17) by mild oxydation under physiological condition.
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犬伏 康夫, 正木 幸雄, 松本 佐市, 鷹見 文隆
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Total syntheses of optically active natural phaeanthine(1a), isotetrandrine(1b), and tetrandrine(1c) have been now accomplished through Route B. The intermediate coclaurine type base(14: racemate) was first synthesized, resolved, and N-methylated. The Ullmann condensation of the resulting optically active base(15) with the phenylethyl amine(17) afforded the diphenyl ether(18) which after debenzylation, was submitted to the second Ullmann condensation with the compound(20). The product(21) was then transformed to the cycloamide(24) via the compound(23) by the p-nitrophenyl ester method. The Bischler-Napieralski reactin of the resulting amide(24) gave the dihydroisoquinoline(25). Reduction of the compound(25) with NaBH_4, followed by N-methylation, gave a diastereomeric mixture consisting of isotetrandrine and phaeanthine. Separation of each diastereomer was effected by the aid of different solubilities of the picrates. The synthesized isotetrandrine and phaeanthine were identical with authentic samples of these alkaloids, respectively in all respects including their specific rotations. On the other hand, reduction of the compound(25; racemate) with Zn-dil.-H_2SO_4 gave chiefly dl-tetrandrine. Since dl-tetrandrine has been isolated from the natural source and resolved, this synthesis implies the total synthesis of natural tetrandrine.
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入江 寛, 岸本 禎二, 上尾 庄次郎
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The total synthesis of (±)-ochotensine (I) and (±)-ochotensimine (II) has been accomplished by a sequence of reactions including the Pictet-Spengler condensation of 4,5-methylenedioxyindan-1,2-dione (XXV) with 3-hydroxy-4-methoxy- and 3,4-dihydroxyphenethylamine, respectively. Prior to an approach to ochotensimine, an isomeric compound (IV) was first prepared as a model compound. The Pictet-Spengler condensation of the indandione (XIII) with the hydrobromide of the amine (XIV) in anhydrous ethanol gave the spiro-isoquinoline (XVII), which was O-methylated with an excess of diazomethane and N-methylated by the Eschweiler-Clarke method to yield (XIX). The Wittig reaction on (XIX) with methylenetriphenylphosphorane gave (IV). For the synthesis of ochotensimine, the indandione (XXV), which was prepared from ovanilline in twelve steps, was subjected to the same series of reactions as above. The Wittig reaction on (XXVII) gave (XXVIII) which was treated with formalin followed by sodium borohydride, to afford (±)-ochotensimine (II). Next, the Pictet-Spengler condensation of the indandione (XIII) with (XV) gave the spiro-isoquinoline (XXIX). After N-methylation, the phenolic hydroxyl group of (XXX) was protected as its methoxymethyl ether. The Wittig reaction with the protected compound (XXXI) and hydrolysis of the reaction product furnished the isomer (III) of ochotensine. In the same manner, the indandione (XXV) was condensed with (XV) to give the key intermediate (XXXIII) which was N-methylated and O-methoxymethylated. The resulting protected compound (XXXV) was then converted into the exomethylene derivative (XXXVI) and hydrolyzed with dilute hydrochloric acid to give (±)-ochotensine, identical with an authentic sample of (+)-ochotensine in spectral properties and t.l.c.
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亀谷 哲治, 福本 圭一郎, 八木 治彦, 佐藤 文夫
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Recently, several morphinandienone- and androcymbine-type alkaloids were isolated, but the general approach to these alkaloids has not yet been investigated. Therefore, we are currently investigating the syntheses of morphinandienone and androcymbine-type compounds, and we wish to report the syntheses of O-methylflavinanthine (XIX), amurine (VIII) and demethoxy-O-methylandrocymbine (XIV) by the application of Pschorr reaction. It is noteworthy that this modified Pschorr reaction supplies the useful and important ways for the syntheses of many isoquinoline alkaloids, such as proaporphine, homoproaporphine, erythrina, protostephanine and Amaryllidaceae alkaloids.
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真下 喜世彦, 佐藤 泰彦
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A synthesis of rac-ajmaline and -isoajmaline is described. As a preliminary to the synthesis of ajmaline-sarpagine group of alkaloids, Yoneda in our laboratory has recently reported a synthesis of compound (XVI) (Chart-I), representing the fundamental skeleton of the abovementioned alkaloids. In a model experiment for our present study, we converted the intermediate compound (VIIIa) in the above synthesis to (XVIII) by applying Corey's method followed by HAlCl_2 reduction. For the synthesis of ajmaline (VIIIa) was first cyanomethylated to furnish (XIX) (Chart-2), which was then treated as above to give (XXIII). The latter was proved to be identical with the intermediate (XXVIIIa) (Chart-3) in Masamune's elegant total synthesis of ajmaline. Synthesis of isoajmaline was achieved by first introducing α-cyano-n-propyl side-chain to (VIIIa) to afford (XXXIII) (Chart-4) and processed similary to give (XXXVIII), which was found to be identical with the compound (XLIIa) (Chart-5) used as a relay substance prepared from isoajmaline.
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伴 義雄, 若松 武, 池崎 宗克, 藤本 康雄, 大石 武
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The total synthesis of dl-ibogamine (Ia) and dl-ibogaine (Ic), the representative members of these alkaloids, and of the corresponding C-4 epimers were already achived by Buchi, Nagata, Kutney and Sallay, independently. The syntheses of some derivatives having the isoquinuclidine ring system were also reported. In the preliminary experiments for the total synthesis of ibogaine, we reported the syntheses of the keto-ester (XI) and the dl-C_<nor>-C_<20>-hydroxyepiibogamine (Ie). In this communication, we describe the total synthesis of dl-epiibogamine (Ib). The ketal-ester (XIII) was transformed by the action of methylsulfinyl carbanion into the methylsulfinyl adduct, which without isolation, was immediately reduced with aluminum amalgam to the ketal-acetylderivative (XVI). The ethyl-ketal (XVII) obtained from XVI by the Huang-Minlon reduction was hydrolyzed with 10% hydrochloric acid to the desired ethyl-ketone (XVIII). Finally, the phenylhydrazone of XVIII was submitted to the Fischer indolization refluxing with anhydrous formic acid for a half hour to afford dl-epiibogamine (Ib) (m.p. 194-196) after purification by chromatography on alumina eluted with benzene-methylenchloride (1:1). The infrared spectrum of the present product was superimposable on that of the authentic sample kindly provided by Dr. W. Negata. The identity of both samples was further confirmed by the mixed melting point determination, Rf values on TLC and the mass spectral comparison.
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飛永 精照, 小谷 栄一
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A successful approach to the total synthesis of d,l-colchicine, patterned after biogenetical scheme by Robinson and Anet hypothesis, was made. Starting from 4,3'-diacetoxy-3,4',5'-trimethoxy-chalcone 9, after two step reduction compound 11 was oxidized by FeCl_3 to yield phenol coupling product, a spiro-dienone 12 in good yield. Partial reduction of the dienone 12 yield spiro-enone 15. The reaction of iodomethyl zinc iodide with compound 15 followed by Jones oxidation cyclopropane deriv. 24 was obtained. The successfull conversion 24 to 25 and 26 was done by acid treatment, in which the cyclopropane cleavage followed by aryl rearrengement are take place successively. Compound 25 and 26 could be easily convert to the tropolone 28 which was already synthesized by A. E. Eschenmoser and transformed to d,l-cochicine. The expecting final reaction to the total synthesis, cycloheptenone 27 to the tropolone 28 is now under the investigation.
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楠本 正一, 岡崎 具視, 大須賀 昭夫, 小竹 無二雄
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A bitter principle, solidagonic acid, C_<22>H_<34>O_4, mp143-144℃, [α]_D-97.6°, was isolated from the root of Solidago altissima L.. The IR, UV and NMR spectral data and the chemical evidences suggested that solidagonic acid is an α,β-unsaturated carboxylic acid having an acetylated secondary hydroxyl group, two trisubstituted double bonds, two vinyl hydrogens, two vinyl methyl groups, one secondary methyl group and two tertiary methyl groups. The locations of the double bond and the acetoxyl group were determinde by introducing the methyl groups followed by dehydrogenations with Se or Pd-C. The structure of solidagonic acid was confirmed by the NMR spectrum of the derived saturated ketone (XIX). The ORD curves of some ketone derivatives (XIX, XXIV and XXX) led to the absolute configuration shown by (III) for solidagonic acid. Two other constituents, kolavenol((XXXIII), 3,5-dinitrobenzoate, C_<27>H_<36>O_6N_2, mp106℃) and kolavenic acid (methyl ester (XXV), C_<21>H_<34>O_2, bp151℃/1mmHg), were isolated. Their structures were deduced in connection with solidagonic acid.
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永田 亘, 若林 利生, 早瀬 善男, 成定 昌幸
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Results of the studies directed to total synthesis of C_<20>-gibberellins are presented. Starting from the tetracyclic enone 2, the key intermediate for our total syntheses of diterpene alkaloids, compound 37 having the ABCE ring system of the gibbane skeleton was synthesized in a stereocontrolled manner and in good yield. Hydrocyanation of the hydrindenone derivative 18 to the cis hydrindanyl carbonitrile 19 was effected in excellent yield with diethylaluminum cyanide in methylene chloride. A new method for formylolefination was successfully applied to the angular carboxaldehydes (33 and 36) giving 34 and 37 in excellent yields. In a model experiment using steroid molecule, a new one-step method for building-up of the BCD ring system was established (42→43). Another model experiment for construction of the AE ring system was accomplished using the tetracyclic secondary amine 46 giving 49. Investigation for conversion of 37 into gibberellin A_<15> is in progress.
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森 謙治, 汐崎 正生, 板谷 信重, 小川 智也, 松井 正直, 住木 諭介
原稿種別: 本文
セッションID: 38
発行日: 1968/09/20
公開日: 2017/08/18
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The first total synthesis of the title compounds, four of the C_<19>-gibberellins, is discussed. The key intermediates are (±)-epigibberic acid (2), the (±)-diketo ester (3), the dienone (4) and gibberellin C (5). Catalytic reduction of the aromatic A-ring of 19 was one of the crucial steps. A model experiment employing 23 afforded 24 which showed an analogous ORD curve as that of the known 25. In the case of 19, the desired 3 was obtained in 4% yield. Conversion of 30 into 31 was successfully carried out in 12% yield by Pd-C catalyzed double bond migration. The carbomethoxylation of 35 followed by removal of the ketal protective group gave crystalline 37 in 11.4% yield after chromatographic purification. Alkaline hydrolysis of gibberellin A_4 methyl ester (42) afforded gibberellin A_4 (7) and its 2-(eq)-epimer (43).
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田原 昭, 大澤 富彦, 星野 修
原稿種別: 本文
セッションID: 39
発行日: 1968/09/20
公開日: 2017/08/18
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Although large amounts of 1-abietic acid (1) are readily available from many kinds of common japanese pine tree, the acid itself has not remarkable physiological activities. However, many natural diterpenoids, such as gibberellin and diterpenoid alkaloid, closely related to (1) have been widely known as noticeable substance. Accordingly, studies on chemical conversion of (1) to the useful compounds have been undertaken in our laboratory. In this report, abietic acid skeleton is transformed into compounds (9) and (46), regarded as the basic structure of gibberellin and aconitine type alkaloid respectively. A synthesis of c-homohydrofluorene (9) has been realized by opening and successive ring closure of B/C-ring juncture of Δ^<8,9>-unsaturated ester (4) prepared from (1). Furthermore, a standard trans-A/B-ring hydrofluorene (30) is synthesized from (9). In comparison with this standard, structures of hydrofluorene (36), (38) and (39) previously prepared by alkaline treatment of cis-diketo ester (32) have been confirmed to have cis-A/B-ring fusion. Otherwise, stereochemical analysis on catalytic hydrogenation of unsaturated hydrofluorene (37) and (41) is also carried out. Successively, Δ^<8,9>-unsaturated ether (43) obtained from epoxy compound (42) was treated as in previous ring construction. Under the sterical influence of the ether bridge, the condensation of the diketo ether (45) lead to afford an aconitine type skeleton, which is in contrast to the previous case.
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藤田 栄一, 藤多 哲朗, 片山 肇, 渋谷 雅之, 長尾 善光
原稿種別: 本文
セッションID: 40
発行日: 1968/09/20
公開日: 2017/08/18
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The transformations of enmein into (-)-isokaurene, beyerane, diterpene alkaloids and gibbane derivatives have been attempted. The transformation started with compounds 3〜8 prepared by the acyloin condensation reaction of unsaturated lactone ester 2 which had been derived from enmein. Ketoaldehyde 36, an oxidation product of 4, on Wolff-Kishner reductions gave (-)-kaurane, (-)-isokaurene and (-)-kaurene. The ratio of the products was due to the reaction condition. The treatment of hemiketal 40 with zinc, acetic acid and hydrochloric acid resulted in the formation of beyerane derivatives 42 and 43. Upon the photosensitized oxidation of 40 an allyl alcohol 29 was yielded. Further conversion of 29 into triol 26 has been attemped. The benzylic acid rearrangement of 3 yielded compound 18, which was converted into 24 via four steps of reactions.
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野副 重男, 平井 功一, 鈴木 和夫, 奥田 重信, 津田 恭介
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セッションID: 41
発行日: 1968/09/20
公開日: 2017/08/18
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The complete molecular structure of siccanin (I), a physiologically active compound isolated from the cultured broth of Helminthosporium siccans Drechsler, which is a parasitic organism of rye-grass, Lolium multifolium Lam. was established by three dimensional X-ray analysis. In order to seek the biogenetical intermediates or related compounds of siccanin, the screening of the prenylphenols by autoradiography and by color reaction with diazonium salt solution was attempted. Twelve prenylphenol derivatives have been isolated from the cultured broth and micellium of the fungi. The structure of siccanochromene-A (IV) was elucidated from the physiocochemical properties as well as by the chemical correlation through the compound V, which in turn was synthesized from dihydro-α-ionone. Siccanochromene-B, -C, -D, and -F were assigned structures (VII), (IX), (X), and (XII) respectively by the chemical reactions and by spectral properties. The acidic fraction was esterified with diazomethane and chromatographed. Three constituents were found to be present. These compounds are shown to possess structure XIII, XV, and XIX respectively. dl-siccanochromene-A was synthesized from compound XXIX, by five steps chemical reaction. Biosynthesis of siccanin and siccanochromenes are now under investigation.
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津田 喜典, 藤本 琢憲, 森本 明
原稿種別: 本文
セッションID: 42
発行日: 1968/09/20
公開日: 2017/08/18
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Five triterpenoids containing conjugated ketone chromophor were newly isolated-four (A, B, C, and E) from L. clavatum and one (D) from L. serratum, -and characterized. Their structures and stereochemistry were elucidated as 16-oxodiepiserratenediol (1), 16-oxoepiserratenediol (2), 16-oxoserratenediol (3), 16-oxoserratriol (4), and 16-oxolycoclavanol(5), respectively, based on spectroscopic and chemical evidence, wherein several new methods in solving the structural and steric problems were discussed: i.e., i) Application of TH-effect, ii) NMR classification of acetonide types, iii) Alkaline treatment and LAH reduction of 23 or 24-monotosylate. Particularly, the last method had a great advantage to elucidate the stereochemistry of substituents at ring A of poly-hydroxylated triterpenoid by noticing the key-product, an oxetane (18) or a seco-compound (20). 3-Keto-23 or 24-tosylate, (23) and (24), on treatment with t-BuOK, gave novel cyclobutanone derivatives, (25) and (26), which showed strong positive and negative Cotton effect corresponding to its stereochemistry, thus giving a new chemical method for determination of the position of tosyloxy group.
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北川 勲, 北沢 清, 堀 清美, 吉岡 一郎
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セッションID: 43
発行日: 1968/09/20
公開日: 2017/08/18
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Interested in photochemical reactions being applied in the biogenetic type chemical derivation of natural products, we have investigated the photochemical transformation of some triterpenoids. It has been clarified that the photooxidation of oleanolic acid (I) in an acidic medium afforded 12α-hydroxy- and 11α,12α-epoxy-oleanolic lactones (VIIIa, VIIa), the latter having the identical epoxy-lactone moiety with eupteleogenin (II), while the similar oxidation of erythrodiol (XVIIIa) yielded 11α,12α:13β,28-diepoxy compound (XIXa) in addition to 11α,12α-epoxy-taraxerol derivative (XXa). Some interesting features found during the course of the study on the above photoreaction products have been discussed, and in addition, priverogenin B (XXVIb), a genuine sapogenin of Primula sp., has been derived from camelliagenin A (XXIb). Furthermore, the photolytic decarboxylation of leucotylic acid derivatives (XXVII) has been investigated as a model experiment leading to the exo-methylene compounds (XXVIII). Finally, it has been suggested being possible to synthesize eupteleogenin (II) partially in a few steps, following the above-developed photoreactions, starting from e.g. spergulagenic acid (XXIX).
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上田 博之, 塩島 憲治, 荒井 洋子, 笠間 俊男, 梶井 健造
原稿種別: 本文
セッションID: 44
発行日: 1968/09/20
公開日: 2017/08/18
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Although 30 kinds of triterpenoids having the hopane, isohopane, 30-norhopane and 30-norisohopane skeletons have been isolated from the ferns, lichens and other plants, there remain some problem to resolve on the configuration of their side chain, i.e. the configuration at C-21 and C-22. Configuration at C-21: Adipedatol (I) is a fern triterpenoid of the 30-norhopane group having a hemiketal linkage between C-22 and C-28. The successful correlation of (I) to hydroxyhopane (V) and hydroxyisohopane (VI) has been established as shown in Chart 1. The results strongly suggest that hydroxyhopane and other triterpenoids of the hopane group, such as hydroxyhopanone, diploptene, neriifoliol, dryocrassol, dustanin and adiantone, have 21βH-configuration, and hydroxyisohopane has 21αH-configuration. Configuration at C-22: Dryocrassol (XI), isolated from Dryopteris crassirhizoma and found to be C-22 epimer of neriifoliol (X), has derived to adiantol B acetate (XV), a derivative of which is going to be subjected to X-ray analysis. Isoadiantol B (XVII), a constituent of Adiantum monochlamys, can be represented to have 22S-configuration according to an analogy to 20-hydroxypregnanes.
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原稿種別: 索引
p.
336-338
発行日: 1968/09/20
公開日: 2017/08/18
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原稿種別: 付録等
p.
App2-
発行日: 1968/09/20
公開日: 2017/08/18
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