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佐伯 博道, 岩重 忠博, 大木 英二
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1,2: 3,4-Di-O-isopropylidene-α-D-galacto-hexodialdo-1,5-pyranose (2), which was easily prepared from D-galactose, was treated with sodium cyanide in aqueous methanol and the resulting cyanohydrin mixture was tosylated to give 1,2: 3,4-di-O-isopropylidene-6-O-tosyl-L-glycero-(5), mp152-154°, [α]^<20>_D-46.1°, and -D-glycero-α-D-galacto-heptopyranurononitrile (6), mp145-145.5°, [α]^<20>_D-110.4°. Lithium aluminum hydride reduction of these tosylates (5 and 6), followed by acetylation, yielded D-glycero-N-acetylepimine (9), syrup of [α]^<21>_D-50.9°, and L-glycero-N-acetylepimine (10), mp95-96°, [α]^<21>_D-121.0°, respectively. The D-glycero-N-acetylepimine (9) thereby obtained was treated in warm acetic acid to give 6-acetamido-7-O-acetyl-6-deoxy-1,2: 3,4-di-O-isopropylidene-D-glycero-α-D-galacto-heptopyranose (30) as powder of [α]^<21>_D-47.9°. Deacetylation of 30 with sodium methoxide yielded a 7-deacetyl derivative (32), amorphous powder of [α]^<21>_D-41.5°. Pfitzner-Moffatt oxidation of 32, followed by treatment of the resulting 7-oxo derivative (34) with methylmagnesium bromide in ether gave 6-acetamido-6,8-dideoxy-1,2: 3,4-di-O-isopropylidene-L-threo-α-D-galacto-octopyranose (36) as a syrup. 36 was converted into its D-erythro derivative (38), mp165-166°, [α]^<21>_D-162.7°, by oxidation with chromic anhydride in pyridine and successive reduction with sodium borohydride. The latter compound (38) was identified with an N-acetyl-1,2: 3,4-di-O-isopropylidene derivative of lincosamine which constitutes a sugar component of an antibacterial antibiotic, lincomycin.
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奥田 拓男, 魚部 健市, 大崎 健次, 多賀 徹
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Coriose, isolated from Coriaria japonica A. Gray, was found to have the structure (I). Although this sugar is easily crystallized to yield one form of crystals, it is very rapidly converted to the equilibrated mixtures in the solution, as exhibited by the fast mutarotation and the transformation of the NMR spectra. On acylation of coriose with acyl chloride, pentabenzoate (XI) and pentaacetate (XIII) which are regarded as the furanoids are produced. However, mixtures containing the pyranoid acetate (XII) is obtained on the acetylation with acetic anhydride-pyridine. The α-furanose structure (Fig. 1) in the crystalline state, which is regarded as being unstable based on the conformational analysis, has been determined by the X-ray analysis. Determination of mutarotated coriose by the NMR spectra in DMSO-d_6, and by the gas chromatography of trimethylsilyl ethers of the pyridine solution, and also of the syrupy mixtures of coriose with other sugars and polyalcohols, has been attempted. The two-step trimethylsilylation of crystalline coriose leading to two final products as shown by VII→XIV→XV→XVI is also exhibited by the corresponding peaks in the gas chromatograms of trimethylsilylated products from the equilibrated coriose. Fairly high amounts of the furanoses and the keto-form in the equilibrated mixtures are exhibited by the NMR spectra and by the gas chromatograms.
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若宮 建昭, 芝 哲夫, 金子 武夫, 永田 明穂, 田家 照生, 榊原 秀夫
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A new antibiotic, tuberactinomycin(TUM), has been obtained from the broth filtrate of Streptomyces griseoverticillatus var. tuberacticus which was isolated from a soil sample collected at Ohito-cho, Shizuoka-ken. TUM is a basic peptide and effective against tubercular bacilli. TUM is composed of serine, α,β-diaminopropionic acid, and two unknown amino acids A and B. Hydrolysis of 2,4-dinitrophenylated TUM gave DNP-A compound which was absorbed at 1780cm^<-1> due to γ-lactone in IR spectrum. The amino acid A was found to be a basic γ-hydroxy amino acid of a molecular formula C_6H_<14>O_3N_2. Furthermore, carbobenzoxy A compound was isolated from carbobenzoxylated product of the hydrolyzate of TUM. From the results of elementary analysis, NMR, ORD etc. of A and its carbobenzoxylated derivative, it is now concluded that the structure of the new amino acid A should be assigned to threo-γ-hydroxy-L-β-lysine. When TUM was treated with conc. H_2SO_4, and then hydrolyzed partially, erythro-γ-hydroxy-L-β-lysine was obtained. The structure determination and stereochemistry of both isomers will be discussed in detail.
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瀬崎 正次, 近藤 信一, 前田 謙二, 梅沢 浜夫, 大野 雅二
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Aquayamycin, found in 1967, is an antibiotic isolated from Streptomyces misawanensis, and one of the most potent inhibitors of tyrosine hydroxylase and dopamine β-hydroxylase and active against Gram positive bacteria. Aquayamycin (1), n-butyl acetate solvate C_<25>H_<26>O_<10>・C_6H_<12>O_2, easily affords a triacetyl derivative. Hydrogenation of aquayamycin affords a dihydro derivative and acid treatment of dihydroaquayamycin affords a dehydrated product (3). On the other hand, treatment of aquayamycin with barium hydroxide affords an another dehydrated product (4a). Zinc-dust distillation of aquayamycin affords a naphthacene derivative. These results suggest that C-D ring junction of aquayamycin must be elaborated not only to afford benz(α)anthraquinone but also naphthacenequinone upon reaction conditions. The substituent of A ring has been shown to be 6-methyl-4,5-dihydroxy-tetrahydropyran by nmr spectra. Treatment of aquayamycin with 8% methanolic hydrogen chloride affords an anthraquinone methyl ester (7a). Treatment of 7a with base affords an acid (8), which affords pentaacetyl derivative of 4a by the treatment of acetic anhydride and pyridine at 105°. An interesting photochemical transformation of aquayamycin was observed. UV irradiation of aquayamycin in methanol affords an anthraquinone derivative (9), which is transformed into 4a by treatment with pyridine. Such photochemical rearrangement is understandable if C-D ring junction is trans. These evidences reasonably supports a unique naphthoquinone derivative of aquayamycin as shown 1.
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小川 安昭, 竹内 節男, 米原 弘
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An acidic lipophilic antibiotic was isolated from the fermentea broth of the Streptomyces sp. No. 8403-MC_1. The antibiotic was identified with PA-132. Based on the chemical and spectroscopic evidences, it has an unique pentalene skeleton with a seven membered glycidic lactone as shown in Fig. 3 and was named pentalenolactone. The X-ray analisis of pentalenolactone 2-bromoethylamine salt is now under investigation.
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小山 裕三, 岡田 健二
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The crystal structure of Adiantol B bromoacetate (I), Isozygosporin A mono-p-bromo-benzoate (II), and Silver polyetherin A (III) have been determined by X-ray diffraction methods. The crystal structures have been solved by a programme for the automatic heavy-atom analysis, written by Koyama and Okada for the C.D.C. 3600 computer, which leads from a heavy atom position to the positions of all atoms without any chemical assumptions. The programme consists of two parts and the first part (A part) selectes from the list of peak positions, which were stored in the computer, a set of atomic sites to be included in the next Fourier calculations. The second part (B part) selectes from the atoms, which were found in (A), a set of atomic sites to be inserted in the next cycle. Selection of the atomic sites in (A) is based on the "reasonable" interatomic distances (1.1〜1.7A) between neighbouring light-atom peaks, and that of (B) is based on the temperature factor (B>10.0A^2) only. The process can repeate cyclically till all atoms of the molecule will be determined. The programme will solve the structures in all triclinic, monoclinic, and orthorhombic space groups. The absolute configurations of Adiantol B bromoacetate, Isozygosporin A mono-p-bromo-benzoate, and Silver polyetherin A have been determined by the anomalous dispersion method.
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亀谷 哲治, 福本 圭一郎, 八木 治彦, 井原 正隆, 小塚 厚人, 小泉 益男, 八巻 一彌, 菅原 勉, 本多 利雄
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Total syntheses of (±)-galanthamine (I-A) and thebaine (III-A)-a formal total synthesis of morphine (IV)-are discussed. Thus, phenol oxidation of the amide (XVI) with K_3Fe(CN)_6 gave the enone (XVII) (40%), which was reduced with LiAlH_4 to afford (±)-galanthamine (I-A) and (±)-epigalanthamine (I-B). Pschorr reaction of the (-)-aminoisoquinoline (XXV-A) and (+)-aminoisoquinoline (XXV-B) gave salutaridine (II-A) and sinoacutine (II-B), respectively, former of which was reduced to salutaridinol (XXVII-A), followed by acid treatment to afford thebaine (III-A). This means a formal total synthesis of morphine (IV). Phenol oxidation of reticuline (XXIX) gave the dienone (XXXI), which was also obtained by Pschorr reaction of the aminoisoquinoline. This dienone was isolated from Corydalis pallida var. tenuis and named "pallidine (VII)" by us.
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犬伏 康夫, 井深 俊郎, 北野 正彦
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Total synthesis of cepharamine (3), which is closely related in skeleton to morphinan (1) and the functionally least complicated member of hasubanan alkaloids, was attempted. The synthesis of the skeletal ring system, (±)-3,4-dimethoxy-N-methyl-hasubanan (13) has been reported in a previous publication. In the present synthesis, the Robinson annelation reaction; the route (b), the synthesis of the compound (20) from the keto nitrile (15); was successfully modified. Direction of enolmethylation of the diketones; the compound (29) possessing the lactam heterocycle and the compound (34) possessing the ethanamine bridge; was examined and it was shown that enolmethylation of the diketone (29) with MeOH-BF_3 brought the compound into the direction favorable to the cepharamine synthesis. Partial demethylation, followed by acetylation and then deketalization gave the ketoacetate (38). Successive treatment of the compound (38) with Br_2 and NaOAc in AcOH afforded the diketone (39), which was enolmethylated with MeOH-BF_3 to give oxocepharamine acetate (40). Lithium aluminum hydride reduction of the compound (40), followed by oxidation with DMSO gave (±)-cepharamine which was found to be identical with natural cepharamine in terms of i.r., n.m.r., and mass spectra and t.l.c. behavior.
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柿本 七郎, 勝井 信勝, 一戸 良行, 山口 槙子
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Miyaconitine (I) and Miyaconitinone (II), the major alkaloids from Aconitum miyabei Nakai, have previously proposed a tentative structures. We now report that the alkaloids I and II would be represented more preferably as I and II. The high resolution mass spectra of I and II indicate the previous molecular formulas to be revised to C_<23>H_<29>O_6N and C_<23>H_<27>O_6N, respectively. The n.m.r. spectra confirm the presence of an acetoxyl, a tertiary methyl, an exomethylene and N-methyl groups in each molecule. It is confirmed that there are an α-ketol in I and an α-diketone in II. Compound I would involve a partial structure CH_3COOCH-C(=CH_2)-C-CH(OH)-CO-as well as a tertiary hydroxyl group and transannular carbonyl system by chemical reactions. These alkaloids belong to C_<20>H_<29>N fundamental base having the same skeleton as songorine and luciduscline. Stereochemistry of I and II was discussed.
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山崎 和男, 三川 潮, 柴田 承二
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Using Ephedra distachya L. fed with ^<15>N-phenylalanine, ^<15>N-alanine, ^<14>C-formate, methionine(^<14>CH_3) and ω-aminoacetophenone (Carbonyl^<14>C), Shibata, Imaseki and Yamazaki proposed previously the pathway(Fig 5) for the biosynthesis of 1-ephedrine. On our renewed experiments, it has been found that phenylalanine-2^<14>C was not incorporated into ephedrine, whereas ^3H labelled benzene ring and ^<14>C at the 3-position of phenylalanine were incorporated into the corresponding positions of ephedrine. It has also been shown that ^<14>C-labelled benzoic acid and benzaldehyde were transferred into ephedrine with a very high incorporation ratio. The stereochemistry at the β-position of 1-ephedrine side chain which is reversed to that of L-phenylalanine would be explained by the new biosynthetic scheme which involves the condensation of φ-C_1 and C_2-N units (Fig 7).
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尾中 忠正
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The concept of the simple synthesis which was examplified last year by the present author, is further demonstrated by the synthesis of two different series of alkaloids having an interesting skeletal structure (pyrrolidino [3,2-b] quinazolone and furo [2,3-b] indole). I Syntheses of Three Pyrrolidino [3,2-b] quinazolone Alkaloids A general and widely applicable threestep synthesis of pyrrolidino [3,2-b] quinazolone alkaloid has been established. Condensation of anthranilic acid and its derivative(10a,b) with O-methylbutyrolactim(14) proceeded readily to afford compounds(12a,b) with pyrrolidino [3,2-b] quinazolone ring system. The NBS bromination of these products, followed by the substitution with appropriate nucleophiles completed the synthesis with the production of acetylvasicinone(15a), anisessine(6), 16a-2 and "sessiflorine"(9). The identity of synthesized vasicinone(4) and anisessine with natural specimens confirms the position of the NBS bromination and proves the correctness of the proposed structure(6) of anisessine. Natural sessiflorine, on the contrary, is not identical with the synthesized sample posessing the structure(9). And the constitution previously assigned to sessiflorine is revised to 17 by the comparison of spectral data of synthesized and natural sessiflorine. II Synthesis of Furo [2,3-b] indole Alkaloid Physovenine(19) Consideration of general approach to the synthesis of furo and pyrro-[2,3-b] indole led us to examine a new type of construction of these ring systems utilizing the key reaction represented by the conversion from 23 to 24. The Grignard compound of 5-methoxyskatole(27) was reacted with ethylene oxide to furnish oily nor-physovenmethol(28), which could be readily methylated to physovenmethol(29). Two step convertion of 29 to physovenine(19) has already been achieved, and therefore our synthesis constitutes a formal five step synthesis of physovenine starting from p-methoxyphenylhydrazine.
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志津里 芳一, 山田 靜之, 平田 義正, 和田 博, 田中 雅
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Alkaloidal components in the following plants of Celastraceae were examined: Euonymus Sieboldiana Blume (japanese name, Mayumi), Euonymus alata Sieb. forma striata Makino (Komayumi), Euonymus alata Sieb. (Nishikigi), Euonymus oxyphylla Miq. (Tsuribana), Euonymus japonica Thumb. (Masaki). A crystalline alkaloid was isolated from Nishikigi. Two crystalline alkaloids, evonine-I (1) and -II (2) were obtained from Mayumi. Structural studies on evonine-I (1) and -II (2) were carried out. Evonine-I (1) and -II (2) were interconvertible. Evonine-I (1) contains two tertiary methyls, a hydroxyl, a ketone carbonyl, and ether (an acetal), two esters due to evoninic acid, and five O-acetyl groups. Hydrolysis of evonine-I (1) afforded evoninic acid (13). From a series of reactions evonine-I (1) was proved to be consisted of evoninic acid (13) and a highly oxygenated C-15, through two ester linkages. By means of chemical and spectral evidence interrelationship of most of the functional groups in evonine-I (1) was established. Further, the partial structure of evonine-I (1) was deduced.
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伴 義雄, 池崎 宗克, 若松 武, 大石 武
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Ibogamine(Ia) and ibogaine(IIa), the representative menbers of these alkaloids, were already synthesized by Buchi, Nagata, Kutney, and Sallay, independently. We also reported the synthesis of dl-epiibogamine. We have now extended our method to the syntheses of dl-ibogamine, dl-ibogaine, dl-epiibogaine, dl-tabernanthine(IIIa), and dl-epitabernanthine(IIIb), which involves separation of the stereoisomers of the penultimate Products(XVI). The Ziegler cyclization of (V) gave a complicated mixture of products, which was separated by chromatography to give two enamines: (VIIIa) mp163-4°and its epimer (VIIIb) mp240-6°. Both enamines were hydrolysed with C-HCl, and the product was esterified with diazomethane to afford the (XIIa) mp70°, and (XIIb) mp66-8°as a mixture. The ketal-ester(XIII) obtained from the (XIIa) was converted by Corey's method to the acetyl derivative(XIV). The Huang-Minlon reduction and subsequent deketalization gave the ketone(XVI) which gave two spots on tlc. Chromatography of (XVI) afforded (XVIa) pic., mp178-180°and (XVIb) pic., mp184-6°. (XVIa) and (XVIb) were obtained by the same treatment of (XIIb) as (XIIa). The Fischer indole cyclization of (XVIa) with phenylhydrazine by anhydrous formic acid gave dl-ibogamine, mp132-4°. On treatment of (XVIb) in a similar way, dl-epiibogamine, mp194-6°, was obtained. This result makes clear the configuration of ethyl group, namely, (XVIa) is exo-ethyl derivative and (XVIb) is endo-ethyl derivative. We also synthesized dl-ibogaine; mp111-5°, dl-epiibogaine; mp179-180°, dl-tabernanthine; mp181-5°and dl-epitabernanthine; mp216-21°, stereospecifically, by use of methoxy substituted phenylhydrazine in stead of phenylhydrazine.
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川松 豊, 杉原 弘貞, 佐々木 希吉, 森本 浩
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I. Synthesis of 2,3-dialkoxy-5-alkyl-1,4-benzoquinone a) 4a and 4b obtained from 1 were oxidized with organic peracids to give 2,3-dimethoxy-(5a) and 2,3-diethoxy-5-methyl-1,4-benzoquinone (5b). b) 9a and 9b obtained from 6 were oxidized in a similar manner to give 5a and 10. II. Synthesis of isoprenoid quinones The authors found two new condensation methods. a) Method using an N-sulfinylamine. A solution of hydroquinone (12), methyl N-sulfinylanthranilate (14) and phytol (13) in dioxane was heated and oxidized with ferric chloride to give 2,3-dimethoxy-5-methyl-6-phytyl-1,4-benzoquinone (15) as well as by-products 16 and 17. The structures of 16 and 17 were made clear and the reaction mechanism was discussed. The results are shown in Table 1. b) Method using a metal. A solution of 5a and X-CH_2-CH=C-CH_3-CH_2-R in petroleum ether was treated with slightly an excess amount of amalgamated zinc at the room temperature to give 18. The product 18 was obtained also from hydroquinone (12). The reaction mechanism and the results are shown in Table 2. III. Stereochemistry of isoprenoid quinones It has been so far known that the steric configuration of the side chain of naturally occurring isoprenoid quinones is all-trans, but synthesized isoprenoid quinones inevitably contain a small amount of the cis-isomer. Then, the authors separated these isomers by the column chromatography to confirm their yields and to compare their NMR spectra with each other. The relationship between the structures of the quinones and the biological activity is also mentioned.
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磯江 幸彦, 勝村 成雄, 玄 亟培, 目 武雄
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Previously, we demonstrated the photo-sensitized oxygenation of β-iond and dehydro β-ionone to dihydroactinidiolide, actinidiolide and actinidol as a model for the biosynthesis of C-11 and C-13 oxygenated compounds. In that case, a novel photo-sensitized oxidation reaction of β-ionol to allenic alcohol was found. In this paper we demonstrated the stereospecific synthesis of loiolide and isomeric allenic ketodiol by using photosensitized oxidation starting from hydroxy-β-ionol. The stereochemistry of natural and synthetic allenic compounds is discussed in view of their synthetic pathways. Vomifoliol, a novel C-13 compound isolated from Rauwolfia vomitolia was also synthesized by photo-sensitized oxygenation. The mechanisms of the formation of C-11, C-13 and C-15 compounds from carotenoids are also discussed.
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杉野目 浩, 佐藤 紀朗, 小野 均, 小島 孝子, 折登 一彦, 正宗 直
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Compared with normal steroids little success has been noted on the functionalization of 18-methyl group in the field of C-nor-D-homosteroids. In this paper, the successful functionalization of 18-methyl groups of C-nor-D-homosteroids with cis as well as trans C/D ring junction by the intramolecular radical processes will be reported. In all cases, jervine or 11-deoxojervine was chosen as the starting material and transformed via several steps into the nitrogen-free compounds, 17α- or 17β-acetyl-12α-etiojervanes, (X and XII) or 17α-acetyletiojervanes (XVIII and XXVI). These were reduced with NaBH_4 to afford the corresponding 20-ols which were then submitted to the Barton, Hypoiodite and lead tetraacetate reactions. It has been shown that the functionalization of 18-methyl group was possible by the hypoiodite reaction of XVa and the Barton reaction of XXVIIb and afforded 18-oxygenated 12α-etiojervane (XVIa) and 18-oximinoetiojervane (XXX) respectively. (XVIa) may be valuable as a relay compound in transforming jerveratrum alkaloids into fritillaria alkaloids, e.g., verticine and (XXX) would be useful intermediate for C-nor-D-homo-analogue of aldosterone. On the other hand, in hypoiodite and lead tetraacetate reactions of 20-ol (XIXa) derived from (XVIII), it has been observed that the products from β-scission of secondary alkoxyl radical overwhelmingly predominated over hydrogen abstraction. In the course of these studies, some unusual products were obtained. Some aspects of these intriguing variation of the reactions will be discussed.
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三橋 博, 林 紘司, 福岡 正道
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C/D cis polyhydroxy-pregnanes with the 1,2-vicinal glycol have been isolated from Digitalis spp., Adonis spp., and from many genera in Asclepiadacae. This report deals with the synthesis of tomentogenin from hecogenin and with the structure of marsaenin and stephanol, isolated from Marsdenia cundurango Reich and Stephanotis japonica Makino, respectively. Partial synthesis of tomentogenin isolated from Marsdenia tomentosa Dence, was achieved by the reduction of the bisepoxide (V), and this key intermediate(V) was prepared by the introduction of epoxide to the β position of 3β,12β-diacetoxy-14β,15β-epoxy-5α-pregn-16-en-20-one(IV). Marsdenin was given the structure of 3β,8β,11α,12β,14β-pentahydroxy-17-isopregn-5-en-20-one(XI) and stephanol was assigned that of 3β,8β,11α,12β,14β,17β,20-heptahydroxy-pregn-5-ene(XV), on the bases of chemical and physical evidences.
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是枝 正人, 守山 弘, 中西 香爾, 今井 俊司, 岡内 哲夫
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I. The structures of the Phytoecdysones The structure of the following phytoecdysones are discussed. As all ecdysones are polyols, the dibenzoate chirality rule or its extention provide a very convenient method for configurational and conformational studies of such compounds. a) Ajugasterone C (2). The dibenzoate chirality rule, as applied to (6) and the model compound (8), indicates that it can be extended to 1,2,6-triols and establishes the 11-OH configuration to be a. b) Ajugasterone D. Preliminary data show this to be structurally isomeric to ajugasterone B (9) at C_<24>-C_<29>. c) Ponasterone C (15). The previous structure, 24-hydroxy-(10) has been revised to (15). Optical and nmr (NOE) data of other 5-hydroxy-7-en -6-one have been measured in conjunction with structural studies. Ponasterone B ((10) and (14)), the structure of which has been reconfirmed, is thus the only ecdysone having 2α and 3α hydroxy groups. d) Stachysterone A (24), B (25), C (28) and D (29). Stachysterone A is the first ecdysone to have a rearranged skeleton. e) Ajugalactone (30). The activity of this compound possessing a 14β-OH appears to be quite unusual. II. Stereochemistry of the side-chain The configuration at C-22 in the majority of ecdysones has been established as being R. The C-20 configuration will be discussed. III. Metabolism of choesterol and ecdysones in B. mori Bioorganic studies (injection or feeding) employing fifth instar larvae of Bombyx mori, 23,24-^3H-a-ecdysone and 4-^<14>C-cholesterol enables one to propose Scheme 1. It is to be noted, besides other results, that α- and β-ecdysones are biosynthesized from cholesterol in the posterior half of the insect which does not contain the prothoracic gland.
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松浦 輝男, 川井 正雄, 中島 路可, 仏願 保男
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発行日: 1969/09/01
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The bitter principles were isolated from Physalis Alkekengi var Francheti, and named physalin A and physalin B. Physalin A (C_<28>H_<30>O_<10>・CH_4O, mp. 260-2°, from methanol; C_<28>H_<30>O_<10>・C_3H_6O, mp. 265-6°, from acetone) (I) was converted into its tetrahydro-derivative (II), which was treated with Br_2-AcONa, affording an acetoxybromide (VII). An X-ray crystallographic analysis was carried out and the structure of the acetoxybromide (VII) was established, from which the structure of physalin A (I) was determined unequivocally. Physalin B (C_<28>H_<30>O_9・CH_4O, mp. 269-72°, from methanol; C_<28>H_<30>O_9・C_3H_6O, mp. 245-50°, from acetone) (VIII) gave an tetrahydro-derivative (X) on catalytic hydrogenation, which was also obtained by the hydrogenation of the acid-treatment product (XII) of physalin A (I). Thus physalin A (I) and physalin B (VIII) were correlated and the structure of the latter was established. Both physalin A and physalin B belong to a new type of C_<28>-steroids, the carbon skeleton of which has following two biogenetically interesting features: i) The C(13)-C(14) bond between rings C and D is broken resulting a nine-membered ring formation. ii) A bond is formed between C(16) and C(24) making a new six-membered carbocycle.
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津田 喜典, 藤本 琢憲, 礒部 公明, 遠藤 雅子
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The structure of lycoclavanin, a 16-oxoserratene group triterpenoid occurring in Lycopodium clavatum, was established as (6) by correlation with 16-oxolycoclavanol (5) transforming the each compound into the same keto-diacetate (12). The stereochemistry of cis-α-glycol grouping in ring E was elucidated by application of dibenzoate chirality rule and by inspection of the chemical shift of C_<17>-H signal. Jones' oxidations of 16-oxolycoclavanol acetonide and 16-oxoserratriol acetonide furnished the same keto-aldehyde (16), which on reduction with sodium borohydride in cold exclusively regenerated 16-oxoserratriol (4), thus providing a simple correlation of these triterpenoids. Stepwise transformation of lycoclavanin (6), and 16-oxolycoclavanol (5) into 16-oxoserratriol (4) was also described. Direct correlation of lycoclavanin (6) and serratenediol (28) was successfully achieved by obtaining the same seco-diol (32) as shown in Chart 4. The transformation from lycoclavanin involves the conversion of cis-1,2-glycol into a ketone via tosylation and a stereoselective cleavage of 1,3-glycol monotosylate as key steps. Finally 16-oxoserratenes were synthesized from the corresponding serratenes by oxidation of the latters with limited amount of t-butyl chromate in benzene at 50-60°. Thus serratenediol diacetate, 21-episerratenediol diacetate, serratriol triacetate, and lycoclavanol triacetate afforded naturally occurring 16-oxoserratenediol (1) diacetate, 16-oxoepiserratenediol (2) diacetate, 16-oxoserratriol (4) triacetate and 16-oxolycoclavanol (5) triacetate, respectively.
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大本 太一, 名取 信策
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As the extension of our work on arundoin and cylindrin from Imperata cylindrica Beauv. var. koenigii Durand et Schinz, hexane extracts of fifty- five species of Gramineae plants shown in Table I have been examined for the characterization of triterpenoids. From forty-six species twenty-seven triterpenoids, including two new compounds (X, XIV) and three new natural products, shown in Chart I were isolated and identified. The structural elucidation of the new compounds will be discussed. As the results wide occurrence of triterpenoids, especially triterpene methyl ether (II, IV, VI, X, XIV, XVII, XIX, XX, XXII) was confirmed. Coexistence of fern-9(11)-ene derivatives (I, II, III, IV) and arbor-(11)-ene derivatives (V, VI, VII, IX, X) in thirteen plants might be interesting from biogenetical point of view. Further discussion on chemotaxonomy of triterpenoids in the family will also be presented.
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上田 博之, 塩島 憲治, 荒井 洋子
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1. Acid induced migration of the migrated hopenes, i.e. filic-3-ene (Ia), adian-5-ene (IIa), fern-9(11)-ene (IIIa), fern-7-ene (IIIc), pteron-14-ene (IVa), neohop-12-ene (Va) gave various products including adian-5(10)-ene (IIb), fern-8-ene (IIIb), 8βH-fern-9(11)-ene (IIId), 9βH-fern-7-ene (IIIe), neohop-13(18)-ene (Vb) and hop-17(21)-ene (VIa) as shown as in Fig. 1. The results are remarkably different from those obtained in a case of migrated oleanenes, such as friedel-3-ene (I'a), glutin-5-ene (II'a), multiflor-7-ene(III'c), taraxer-14-ene (IV'a) and olean-12-ene (V'a). 2. Boiling of fern-9(11)-ene (IIIa) and 8βH-fern-9(11)-ene (IIId) with CrO_3 in acetic acid solutions afforded essentially fern-9(11)-en-12-one (VIII) and 18βH-fern-9(11)-en-12-one (IX), respectively. On the other hand, fern-8-ene (IIIb), fern-7-ene (IIIc) and ferna-7,9(11)-diene reacted with CrO_3 in acetic acid-benzene-CH_2Cl_2 solutions to give various products, such as fern-7-en-11-one (X), fern-9(11)-en-7-one (XI), fern-8-en-11-one (XII), fern-8-en-7-one (XIII), fern-8-en-7,11-dione (XIV), fern-7-en-6-one (XV) and pteron-14-ene-7-one as shown as in a chart. UV, IR, NMR and mass spectra of these compounds are discussed. 3. Correlation of fern-9(11)-ene (IIIa) and arbor-9(11)-ene (III"a) has been established. Fern-8-en-7-one (XIII) was oxidized to ferna-5,8-dien-7-one (XVIII), Zn/AcOH reduction of which gave 25-nor-ferna-5,7,9-trien-7-ol (XIX). 25-Nor-arbora-5,7,9-trien-7-ol (XIX") was also synthesized from arbora-7,9(11)-diene (VII") via arbor-9(11)-en-7-one (XI"), arbor-8-en-7-one (XIII") and arbora-5,8,11-trien-7-one (XVIII"). The fact that (XIX) and (XIX") are proved to be an optical antipode demonstrated that fernane and arborane skeletons have antipodal structures at the ring C, D and E.
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野副 重男, 森崎 益雄
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Mevalonic acid lactone and the chemically synthesized alltrans geranylfarnesyl pyrophosphate (14) are converted into a tricyclic sesterterpene alcohol, ophiobolin F, by the incubation with 100,000xg supernatant fraction from cell free system of eochliobolus heterostophus Mycelia of C. heterostrophus was ground in a mortar with sands in phosphate buffer containing MgCl_2, and the homogenate was centrifuged first at 1,000xg and then at 100,000xg for 1hr. The supernatant enzyme fraction was incubated with 2-^<14>C-MVA in the presence of ATP. It has been found that the enzymic reaction product was identical with ophiobolin F which was found to occur in crude metabolites of the fungi as a very minute amount. The structure and stereochemistry of ophiobolin F was established as 1 by the chemical correlation of it into ophiobolin C (2) whose absolute structure was known. All-trans-geranylfarnesyl pyrophosphate (14) and the terminal cis-isomer (15) were synthesized from geranyllinalool and were incubated with 100,000xg supernatant fraction under the same condition described above. It was found that only all-trans pyrophosphate ester was incorporated into the tricyclic alcohol 17. The data presented provide the first experimental evidence for the intermediary role of geranylfarnesyl pyrophosphate in the sesterterpene biosynthesis
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A. Brossi
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永井 右近, 来海 正輝, 伊賀 福子
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発行日: 1969/09/01
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A number of o-nitrobenzoyl derivatives of optically active secondary alcohols and L-α-amino acids were prepared and found to show Cotton effect around 330nm in their optical rotatory dispersion. Most o-nitrobenzoyl esters of R-configuration showed negative Cotton effect and those of S-configuration showed positive one. But, a few exceptions were observed. Each of the o-nitrobenzoyl esters is considered to be a mixture of conformers C and D, and normally the population of D is negligibly small. But, in such cases as in compounds (II), (XII), and (XV), the population of the conformer D becomes significant. Because the axial isopropyl group in (II) and the angular methyl group in (XII) interact with the nitro group repulsively to result in decreased population of the conformer C. In (XV), the conformer D has significant population because the bulkiness of the substituent L is nearly equal to that of S. So, these exceptional cases can be explained since the conformers C and D have inverse contributions to ORD amplitude according to the sector rule introduced, generally. The sector rule proposed for aliphatic nitro compounds were extended to the Cotton effect of these o-nitribenzoates giving four sectors around the asymmetric centres concerned. All the molecular amplitudes observed were rationalized thus in terms of conformational analysis and the sector rule. All the N-o-nitrobenzoyl L-α-amino acids so far examined showed negative Cotton effect. Conversion of the acids into their eaters or carboxylate ions shifted the amplitudes more positive. These shifts were also interpreted on the basis of their conformation and the sector rule.
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岡本 敏彦, 山口 久夫, 吉田 明
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Various substituted methyl groups were introduced into an angular position of tricyclic phenoles via ring opening of cyclopropanes. Ring opening reactions underwent selectively to give the most stable anionic intermediates. Formation of cyclopropanes Reaction of 1,1-dimethyl-1,2,3,4-tetrahydrophenanthrene (I) with CHBr_3 in aquaous NaOH gave the enone (II). Reduction of II with Zn-AcOH or Li-NH_3 or catalytic reduction over Pd-C afforded the bromo cyclopropane (III) which was characterized by the infrared (IR) spectrum and the nuclear magnetic resonance (nmr) spcetrum and by hydrogenolysis to cyclopropanes. Angular formylation Acetolysis of bromocyclopropane (VI) led to the acetoxy cyclopropane (VII) in a good yield. VII was hydrolized into 4a-formyl compound (IX). Angular cyano methylation, nitromethylation and sulfonomethylation Bromocyclopropane (III) reacted with KCN, NaNO_2 and NaSO_2Ar in DMSO to give (XIII), (XIV) and (XV) respectively in a good yield. Substituted cyclopropanes Bromocyclopropane (III) reacted with CH_3OH, CH_3CO_2H, NH(CH_3)_2 NaN_3 and NaSBz to afford (XVI) (XVII) (XVIII) (XIX) and (XX) respectively which were characterized by IR spectra and nmr spectra. Ring opening of substituted cyclopropanes Substituted cyclopropanes were treated with bases. (XVI), (XVII) and (XX) gave (XXVII) (XXII) and (XXVI) respectively.
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加藤 忠弘, 管野 烝, 種村 満, 鈴木 赳, 北原 喜男
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I Synthesis of α-Chamigrene On the assumption that Chamigrenes (3,4) could be obtained by dehydration and simultaneous cyclization of cis-and trans-monocyclofarnesol (2b,2a), 2a and 2b were treated with iodine in benzene solution and 4 was actually isolated from the reaction mixture with 25% yield. II Cyclization of Monocyclofarnesic Acid In order to obtain the optimum conditions in the acid-catalyzed cyclization of β-monocyclofarnesic acid (10) to α-bicyclofarnesic acid (11), an intermediate which is expected to be of use in synthesis of drimenins(21,22) and levantenolides (32,33), 10 was treated with gaseous boron trifluoride in benzene solution and a new cyclization product (12), an isomer of 11, was isolated. The structure of 12 was determined by chemical degradation and their nmr spectra (table 1). By treatment of 10 with a BF_3-saturated solution of Et_2O-C_6H_6(1: 5) (30°, 24hr), the yield of purified 11 from 10 was improved and increased by up to 55%. III Synthesis of Drimenin The methyl ester (25) was photo-oxidized and the peroxides were reduced (KI) to afford the mixture of hydroxy-esters (26), (27) and oxo-ester (28) which were separated by SiO_2 chromatography. Hydrolysis and simultaneous lactonization of 26 gave the mixture of drimenin (21) and isodrimenin (22). Synthetic approach of polygodial (24) is now under investigation using 30 and 31 which were obtained from 21 by LiAlH_4-reduction. IV Synthetic approach of Levantenolides. 34 was obtained by photo-oxidation of 36 which was derived from 35 and 2,2-Di-3-methylfurylmercury. Cyclization of 34 to levantenolides are being investigated.
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藤田 栄一, 藤多 哲朗, 田岡 学, 片山 肇, 渋谷 雅之, 長尾 善光
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The structure and absolute configuration of sodoponin and epinodosinol have been elucidated as shown in formulas 6 and 10, respectively, on the basis of spectroscopic and chemical evidence. Structure 12 was assigned to ponicidin due to spectroscopic data. Another minor diterpenoid, isodoacetal, was isolated and a tentative structure 13 was proposed based on spectral data. The chemical interconversions, dihydroenmein(14) to enmein(15), and enmein, nodosin(22), oridonin(4) and trichokaurin(5) to isodocarpin(34), have been accomplished.
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村江 達士, 露木 孝彦, 西浜 忠明, 増田 昭三, 高橋 武美
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Three new bitter principles, nigakilactone A, B and C and a known bitter principle, quassin (nigakilactone D), were isolated from Picrasma ailanthoides Planchon (Japanese name: nigaki, Simaroubaceae). Nigakilactone A, B and C were shown to be closely related lactones in the following way. Methylation of nigakilactone A (I), C_<21>H_<30>O_6, m.p. 237.5-238°, with CH_3I-Ag_2O-DMF gave nigakilactone B (II), C_<22>H_<30>O_6, m.p. 278.5°, which was formed by alkaline hydrolysis of nigakilactone C (III), C_<24>H_<34>O_7, m.p. 252.5-253°. The latter compound (III) was obtained on acetylation of II with Ac_2O-pyridine. Nigakilactone A (I) afforded a monoacetate (IV) by acetylation with Ac_2O-pyridine. On oxidation with Na_2Cr_2O_7 in acetic acid, IV yielded a keto-acetate (V). Oxidation of I with CrO_3-pyridine gave an α-ketol (VI), which was oxidized with Bi_2O_3 to afford a diosphenol (VII). On methylation with dimethyl sulfate and alkali, VII gave a methylated diosphenol (VIII), which was shown to be identical with quassin (XI). From these findings, along with the PMR spectrum of I, the structure of nigakilactone A is established as I. PMDR experiment on III, afforded the evidence for the presence of a partial structure (C). These observations lead to the structure III for nigakilactone C and the structure II for nigakilactone B. Nigakilactone D was found to be identical with quassin.
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加藤 夏樹, 柴山 正一, 宗像 桂, 片山 忠二
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Clerodendron tricotomum Thum is shrub that widely distributed in Japan. We extracted two crystalline compounds of feeding repellent, clerodendrin A (C-A) and B (C-B), from the leaves. Clerodendrin A, C_<31>H_<42>O_<12>, and B,C_<31>H_<44>O_<12>, were constituted from (-)-R-2-hydroxy-2-methyl butylic acid, three acetic acids and diterpene as similar to that of clerodin. The structre of the diterpen were deduced from the results of chemical and physico-chemical methods.
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辰野 高司, 藤本 康雄, 森田 悠子
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Red mold wheat caused Fusarium species has been well known as a disease of wheat, barley, oat or rye in many regions. Recently, several kinds of Fusarium sp. were collected from damaged wheat and examined for toxicity. F. nivale (Fn-2) was selected as the isolation of toxic agents, and principle toxins, nivalenol (I), fusarenon-X (II) and nivalenol diacetate (III) were isolated from the charcol-absorbable materials of the F. nivale-growing rice and the cultured filtrate. Pathological examination proved that the fungi-growing rice and these toxins gave necrosis and degeneration of the intestine, bone marrow, lvmp node, thymus and testis of mice, indicating that dividing cells of these tissues were actively injured so called radio-mimetic affections. By the chemical and spectroscopic interconnection with diacetoxy-scirpenol (VI) which has been isolated from the plant parasitic fungus, Fusarium sp. by P. W. Brian and other chemists, the chemical structures of nivalenol, fusarenon-X and nivalenol diacetate was proposed as (I), (II) and (III) respectively. From the mass spectrometrical investigations of these compounds, we tried to confirm the acetylated position of these compounds in addition to chemical and spectroscopic data. Finding the fragment ion peaks which are common to the mass spectra of these compounds, tetrahydroscirpenone and its acetate, we presumed the process of the degradations. We should like to develop this result to a new approach for detection of small amount of these materials which will be contaminated in the cereals.
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小倉 協三, 西野 徳三, 古山 種俊, 瀬戸 秀一
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In the study of the substrate specificity of prenyltransferase which catalyzes "Head to Tail" condensation of C_5-unit in the isoprenoid biosynthesis, it was found that C_6- and C_7-compounds, trans-3-methyl-2-pentenyl pyrophosphate (1b) and trans-3-methyl-2-hexenyl pyrophosphate (1c) were reactive with isopentenyl pyrophosphate in the presence of farnesyl pyrophosphate synthetase to give homo-derivatives of farnesyl pyrophosphate via homo-derivatives of geranyl pyrophosphate (Scheme 1b→2b→3b, 1c→2c→3c). The maximum reaction velocities with 1b and 1c were ca. 1.0 and 0.6 relative to that observed with dimethylallyl pyrophosphate (1a). On the other hand, C_3- and C_4-compounds, (13) and trans-2-butenyl pyrophosphate (17) were not active at all, but they inhibited the reaction of dimethylallyl pyrophosphate with isopentenyl pyrophosphate.
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井上 博之, 上田 伸一, 青木 保彦, 武田 美雄
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(10-^<14>C)-Sweroside (I) was proved to be incorporated into reserpinine (IX) in Vinca major, and quinine (X) in Cinchona succirubra. In an attempt to clarify the biosynthetic routes of several iridoid glucosides, (10-^3H)-bisdesoxydihydrodeacetylasperulosidic acid (XIII) was administrated to several plants containing the glucosides. This labelled compound (XIII) was found to be incorporated into loganin (IV) in Lonicera japonica, verbenalin (XV) in Verbena officinalis, geniposide (XVI) and gardenoside (VIII) in Gardenia jasminoides, asperuloside (VI) in Daphniphyllum macropodum, and aucubin (VII) in Aucuba japonica. (10-^3H)-loganin (IV), (10-^3H)-7-epiloganin (XXVII), (7-^3H)-loganin (IV), and (7-^3H)-7-epiloganin (XXVII) were then fed into Daphniphyllum macropodum, respectively, and the asperuloside (VI) derived from all but the last one (XXVII) was found to be radioactive. (10-^3H)-loganin (IV) was also incorporated into gentiopicroside (III). From these feeding experiments, it was deduced that these iridoid glucosides are biosynthesized along the routes shown in scheme 5.
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稲山 誠一, 川又 健, 柳田 昌一, 関田 恒二郎, 飯高 洋一
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A novel sesquiterpene alkaloid, Pulchellidine (Ia), C_<20>H_<33>O_4N, mp185-186°, was isolated from Gaillardia pulchella Foug. collected near St. Augustin, Florida, along with a minor epimer, Neopulchellidine (Ib), mp131-134°. Pulchellidine (Ia) was converted to a new pseudo-guaianolide, Epipulchellin (IIa), C_<15>H_<22>O_4, mp162-164° by Hofmann degradation of its methiodide. The structures of Ia and IIa were well established on the basis of chemical transformations and several spectral data for the derivatives of III through X. On the other hand, the cultivated species of the same plant (Tenningiku) yielded, on extensive chromatographic separations, Epipulchellin (IIa) mentioned above and an another new epimer, Neopulchellin (IIb), mp166.5-167.5°, along with certain other constituents. The partial syntheses of Ia and Ib were achieved from IIa and IIb, respectively, by addition of piperidin. The stereochemistry of IIa and IIb have been defined as the followings. 1) cis: C_2-α OH/C_4-α OH by sulfites formation and application of Hydson-Klyne rule for dihydro derivatives, VIIa and VIIb. 2) trans: C_1-α H/C_5-β CH_3 from ORD Cotton Effects with Octant rule for dehydro-dihydro derivatives (IIIa, VIIIa and VIIIb), even cis-relationship observed for an equillibrate of VIIIa (VIIIa') and desoxy derivative of VIII (Xa). 3) trans: C_7-α H/C_8-β H for VIIa and cis: C_7-β H/C_8-β H for VIIb on the basis of lactone sector rule with rotations data and reaction rates. 4) C_<10>-α CH_3 and C_<11>-α CH_3 for VIIIa, VIIIb and VIIa, VIIb from certain NMR analyses. 5) C_<11>-α CH_2NC_5H_<10> for Ia and Ib by thermodynamically controlled additions. Finally, the stereostructure of 11, 13-dibromoepipulchellin (X1) evidenced by a complete three-dimensional X-ray analysis confirmed the absolute configuration and sterochemistry described before for Epipulchellin (IIa) as well as Pulchellidine (Ia).
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城戸 英郎, 田中 陽光, 宇田 尚, 吉越 昭
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A) Cubebane-type sesquiterpenoids, α-cubebene (Ia), β-cubebene (Ib) and cubebol (II) were synthesized according to Scheme 1. The unsaturated acid (IX) was prepared from (-)-caran-2-one (V). The diazoketone (X) derived from IX was heated with copper powder giving a mixture of the ketones (XIa-c), Upon hydrogenation XIa gave the saturated ketone (XIIa) identical with the norketone from β-cubebene. Reaction of XIIa with Wittig reagent or with Grignard reagent yielded β-cubebene or cubebol, respectively, and the latter product was dehydrated to α-cubebene. B) The synthesis of methyl epizizanoate (XXVI), whose transformation to other zizaane-type sesquiterpenoids has been reported, is presented. The diolester (XXIV) was synthesized from (+)-camphenecarboxylic acid (XV) as shown in Scheme 2. The monomesylate of XXIV rearranged to the ketoester (XXV) with t-butoxide under mild reaction condition. An equilibrium between XXV and XXVI was attained by prolonged treatment with base. Both ketoesters (XXV and XXVI) were identical with the degradation products of methyl epozizanoate, and XXVI afforded methyl epizizanoate by Wittig reaction.
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高瀬 嘉平, 安東 政義, 七海 憲, 中川 透, 浅尾 豊信
原稿種別: 本文
セッションID: 36
発行日: 1969/09/01
公開日: 2017/08/18
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cis-Decaline-type sesquiterpines, 4α-hydroxyisochamaecynone and (-)occidentalol, were synthesized in the following manner. 1) 4α-Hydroxyisochamaecynone (Ib) and its 4-epi-isomer (VII) were synthesized from the acetylenic ketone (II) which was prepared from 1-santonin through nine step reactions. Enolacetylation of II, followed by epoxidation gave an epoxide (IV), hydrolysis of which gave a hydroxyketone (V). Bromination of V and successive dehydro-bromination afforded 4β-hydroxychamaecynone (VII). Thermal rearrangement of the epoxide (IV), followed by hydrolysis gave a hydroxyketone (IX); the C_4-epimer of V. Bromination of IX and successive dehydro bromination gave 4α-hydroxyisochamaecynone (Ib) which is identical with naturally occurring "hydroxyisochamaecynone". 2) (-)Occidentalol (XVc) and its 7-epi-isomer (XVa) were synthesized from the ketone (XVI) which was derived from 1-santonin. Oxidation of XVI with OsO_4-NaIO_4, followed by oxidation with Ag_2O and then methylation gave an ester (XIX). Bromination of XIX, followed by dehydrobromination gave a mixture of unsaturated ketones (XXII and XXIII), reduction of which with NaBH_4 and succesive dehydration with Al_2O_3-Py afforded a diene (XXV). Treatment of XXV with CH_3MgI afforded an alcohol (XVa), which is not identical with occidentalol. Epimerization of XXV with t-BuOK, followed by hydrolysis and methylation gave a diene(XXVII); the C_7-epimer of the diene (XXV). Treatment of XXVII with CH_3MgI afforded (-)occidentalol (XVc), which is an antipide of naturally occurring (+)occidentalol.
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松本 毅, 白浜 晴久, 市原 耿民, 香川 昌平, 松本 壯二郎, 西田 秀治, 宮野 勝次, 于 世紀, 森田 順平, 小川 純一
原稿種別: 本文
セッションID: 37
発行日: 1969/09/01
公開日: 2017/08/18
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The protoilludane skeleton 40 has been synthesized from a ketoester 13 by a stereospecific route, 4→34→40. A promising intermediate 43 for the synthesis of illudol (or the stereoisomers) has been obtained by a sequence, 34→41→42→43. Further studies toward the total synthesis of illudol are in progress.
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原稿種別: 索引
p.
289-291
発行日: 1969/09/01
公開日: 2017/08/18
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原稿種別: 付録等
p.
App2-
発行日: 1969/09/01
公開日: 2017/08/18
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