著者

亀谷 哲治 鈴木 幸夫 伴 千恵子 三沢 薫 高田 信子 叶田 清 本多 利雄

出版者

天然有機化合物討論会実行委員会

雑誌

天然有機化合物討論会講演要旨集

巻号頁・発行日

vol.29, pp.63-70, 1987

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Chiral cyclopentane derivatives have widely been employed as important starting materials in the syntheses of naturally occurring compounds. Development of an efficient preparation of a chiral cyclopentane derivative from readly available substances with both (+)- and (-)-forms is therefore desirable. We have established an efficient procedure for the preparation of chiral 2-isopropeny1-5-methyl-4-oxocyclo-pentane-1-carboxylate(1) and (2), whose substituents would be transformed into variety of functional groups, from readily avairable (-)- and (+)-carvone. First, the (-)-isomer(1) was employed in the synthesis of (+)-tecomanine (7), an antipodal form of hypoglycemic monoterpene alkaloid, where the aminylium ion-induced cyclization played an important role. Whereas, N-acetyl-L-acosamine (32), found as a structural component of glycosidic antibiotic, was also derived from the (+)-isomer (2) by utilizing the Beckmann rearrangement and Baeyer-Villiger oxidation as key reactions. Finally, Melillo's lactone(34), a key intermediate for the synthesis of carbapenem antibiotic (+)-thienamycin, was prepared from (-)-isomer(1) by manipulation of its substituents in reasonably high-yield.

著者

亀谷 哲治 津吹 政可 日暮 勝之 加藤 正 本多 利雄

出版者

天然有機化合物討論会実行委員会

雑誌

天然有機化合物討論会講演要旨集

巻号頁・発行日

vol.27, pp.176-183, 1985

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The stereocontrolled synthesis of steroid side chain has been developed. The major interest has been forcused on the synthesis of the side chain of ecdysone as well as crustecdysone from 20-oxosteroid via furan derivatives. Reduction of the olefin (21) over palladium-carbon afforded the (20S)-20-furylsteroid (22), stereoselectively, whose hydrogenation over rhodium-alumina, followed by ruthenium tetroxide oxidation and treatment with methylmagnesium bromide, gave the triols (28) and (29) having an ecdysone-type side chain, respectively. The stereoselective reduction of the lactone (33) as a key reaction to give the δ-lactone (35) and the γ-lactone (36), under various conditions has also been investigated. Grignard reaction of both lactones with methylmagnesium bromide led to the synthesis of the tetraol (37) possessing a crustecdysone side chain. The total synthesis of 2-deoxycrustecdysone (3) has also been achieved by application of the above method.

著者

亀谷 哲治 川村 邦昭 津吹 政可 本多 利雄

出版者

The Pharmaceutical Society of Japan

雑誌

Chemical and Pharmaceutical Bulletin (ISSN:00092363)

巻号頁・発行日

vol.33, no.11, pp.4821-4828, 1985-11-25 (Released:2008-03-31)

参考文献数

32

被引用文献数

15 20

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(-)-α-Cuparenone, (17) was synthesized from the olefinic aldehyde (9) by utilizing a rhodium-catalyzed cyclization as a key step. The optically active aldehyde (7) was prepared by employing an asymmetric [2, 3] sigmatropic rearrangement of a quaternary L-prolinol derivative. The aldehyde (7) was also converted into its antipodal form (24) in several steps.

著者

亀谷 哲治

出版者

公益社団法人 日本化学会

雑誌

化学教育 (ISSN:24326542)

巻号頁・発行日

vol.31, no.2, pp.102-106, 1983-04-20 (Released:2017-09-15)

著者

亀谷 哲治 津吹 政可 日暮 勝之 加藤 正 本多 利雄

出版者

天然有機化合物討論会実行委員会

雑誌

天然有機化合物討論会講演要旨集 27 (ISSN:24331856)

巻号頁・発行日

pp.176-183, 1985-09-07 (Released:2017-08-18)

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The stereocontrolled synthesis of steroid side chain has been developed. The major interest has been forcused on the synthesis of the side chain of ecdysone as well as crustecdysone from 20-oxosteroid via furan derivatives. Reduction of the olefin (21) over palladium-carbon afforded the (20S)-20-furylsteroid (22), stereoselectively, whose hydrogenation over rhodium-alumina, followed by ruthenium tetroxide oxidation and treatment with methylmagnesium bromide, gave the triols (28) and (29) having an ecdysone-type side chain, respectively. The stereoselective reduction of the lactone (33) as a key reaction to give the δ-lactone (35) and the γ-lactone (36), under various conditions has also been investigated. Grignard reaction of both lactones with methylmagnesium bromide led to the synthesis of the tetraol (37) possessing a crustecdysone side chain. The total synthesis of 2-deoxycrustecdysone (3) has also been achieved by application of the above method.

著者

井原 正隆 川口 明洋 加藤木 守 千尋 正利 福本 圭一郎 亀谷 哲治

出版者

天然有機化合物討論会実行委員会

雑誌

天然有機化合物討論会講演要旨集 28 (ISSN:24331856)

巻号頁・発行日

pp.339-346, 1986-09-09 (Released:2017-08-18)

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Synthesis of angularly tricyclopentanoid sesquiterpenes, was investigated via tricyclo[7.3.0.0^<1,5>]dodecane derivatives using intramolecular Diels-Alder reaction or intramolecular double Michael reaction as a key step. (1) Highly Stereoselective Total Synthesis of (±)-3-Oxosilphinene via Intramolecular Diels-Alder Reaction-(E,E)-3-(8-Phenylthio-octa-5,7-dien-2-yl)-2-methyl-2-cyclopenten-1-one (19) was prepared from the bromocyclopentenone (16) in three steps. Cycloaddition of 19 gave only one stereoisomer of the tricyclo[7.3.0.0^<1,5>]dodecene (20) having all correct four contiguous asymmetric centers. The cyclo-adduct (20) was converted into the tricyclo[6.3.0.0^<4,8>]undecane (25) via Wolff rearrangement. According to usual procedures, the ester (25) was then transformed into (±)-3-oxosilphinene (1). (2) Synthetic Study of Pentalenene and Pentalenic Acid via Intramolecular Double Michael Reaction-Barbier reaction of 4,4-dimethyl-2-cyclopenten-1-one (34) followed by oxidation with pyridinium chlorochromate gave the enone (36), which was converted into the bis-enone (33) in four steps. Intramolecular double Michael reaction of 33, carried out by heating with trimethylsilyl chloride, triethylamine, and zinc chloride, gave tricyclo[7.3.0.0^<1,5>]dodecanediones (40), which were subjected to Wolff rearrangement to afford the tricyclo[6.3.0.0^<4,8>]undecanes (41) possessing all carbon skeleton of natural products (4 and 5).

著者

亀谷 哲治 鈴木 幸夫 伴 千恵子 三沢 薫 高田 信子 叶田 清 本多 利雄

出版者

天然有機化合物討論会実行委員会

雑誌

天然有機化合物討論会講演要旨集 29 (ISSN:24331856)

巻号頁・発行日

pp.63-70, 1987-07-25 (Released:2017-08-18)

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Chiral cyclopentane derivatives have widely been employed as important starting materials in the syntheses of naturally occurring compounds. Development of an efficient preparation of a chiral cyclopentane derivative from readly available substances with both (+)- and (-)-forms is therefore desirable. We have established an efficient procedure for the preparation of chiral 2-isopropeny1-5-methyl-4-oxocyclo-pentane-1-carboxylate(1) and (2), whose substituents would be transformed into variety of functional groups, from readily avairable (-)- and (+)-carvone. First, the (-)-isomer(1) was employed in the synthesis of (+)-tecomanine (7), an antipodal form of hypoglycemic monoterpene alkaloid, where the aminylium ion-induced cyclization played an important role. Whereas, N-acetyl-L-acosamine (32), found as a structural component of glycosidic antibiotic, was also derived from the (+)-isomer (2) by utilizing the Beckmann rearrangement and Baeyer-Villiger oxidation as key reactions. Finally, Melillo's lactone(34), a key intermediate for the synthesis of carbapenem antibiotic (+)-thienamycin, was prepared from (-)-isomer(1) by manipulation of its substituents in reasonably high-yield.

著者

亀谷 哲治 気賀沢 和雄

出版者

The Society of Synthetic Organic Chemistry, Japan

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.29, no.3, pp.227-236, 1971-03-01 (Released:2009-11-16)

参考文献数

73

被引用文献数

2 1

著者

亀谷 哲治 高野 誠一 寺沢 弘文 武田 裕光

出版者

公益社団法人 日本薬学会

雑誌

YAKUGAKU ZASSHI (ISSN:00316903)

巻号頁・発行日

vol.92, no.7, pp.868-870, 1972-07-25 (Released:2008-05-30)

参考文献数

6

被引用文献数

3 4

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In order to obtain 2, 6-dicyano-7-ethoxycarbonyl-1, 5-dioxo-1, 2, 3, 5-tetrahydroindolizine as an intermediate for the synthesis of camptothecin, Michael condensation of methyl 3-cyano-4-ethoxycarbonyl-1, 2-dihydro-2-oxopyridine-6-carboxylate (V) with acrylonitrile was carried out but failed to afford the objective substance. A similar condensation of V with t-butyl acrylate also resulted in failure. Ethyl 5-cyano-4-ethoxycarbonyl-5-oxo1, 6-dihydro-2-pyridine glyoxylate (VIII) was synthesized by the reaction of 3-cyano-4-ethoxycarbonyl-1, 2-dihydro-2-oxopyridine-6-carboxylic acid chloride with ethyl t-butylmalonate. Although cyclization of VIII to ethyl 6-cyano-1, 2, 3, 5-tetrahydro-1, 3, 5-trioxo-7-indolizine carboxylate (IX) was unsuccessful, Friedlander reaction of VIII with 2-aminobenzaldehyde gave the expected 8-cyano-7-ethoxycarbonyl-9, 11-dihydro-9, 11-dioxoindolizino[1, 2-b]quinoline (X) in one step.

著者

亀谷哲治[ほか]編集

出版者

南江堂

巻号頁・発行日

1969

著者

井原 正隆 川口 明洋 加藤木 守 千尋 正利 福本 圭一郎 亀谷 哲治

出版者

天然有機化合物討論会実行委員会

雑誌

天然有機化合物討論会講演要旨集

巻号頁・発行日

vol.28, pp.339-346, 1986

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Synthesis of angularly tricyclopentanoid sesquiterpenes, was investigated via tricyclo[7.3.0.0^<1,5>]dodecane derivatives using intramolecular Diels-Alder reaction or intramolecular double Michael reaction as a key step. (1) Highly Stereoselective Total Synthesis of (±)-3-Oxosilphinene via Intramolecular Diels-Alder Reaction-(E,E)-3-(8-Phenylthio-octa-5,7-dien-2-yl)-2-methyl-2-cyclopenten-1-one (19) was prepared from the bromocyclopentenone (16) in three steps. Cycloaddition of 19 gave only one stereoisomer of the tricyclo[7.3.0.0^<1,5>]dodecene (20) having all correct four contiguous asymmetric centers. The cyclo-adduct (20) was converted into the tricyclo[6.3.0.0^<4,8>]undecane (25) via Wolff rearrangement. According to usual procedures, the ester (25) was then transformed into (±)-3-oxosilphinene (1). (2) Synthetic Study of Pentalenene and Pentalenic Acid via Intramolecular Double Michael Reaction-Barbier reaction of 4,4-dimethyl-2-cyclopenten-1-one (34) followed by oxidation with pyridinium chlorochromate gave the enone (36), which was converted into the bis-enone (33) in four steps. Intramolecular double Michael reaction of 33, carried out by heating with trimethylsilyl chloride, triethylamine, and zinc chloride, gave tricyclo[7.3.0.0^<1,5>]dodecanediones (40), which were subjected to Wolff rearrangement to afford the tricyclo[6.3.0.0^<4,8>]undecanes (41) possessing all carbon skeleton of natural products (4 and 5).

著者

亀谷 哲治 井原 正隆

出版者

The Society of Synthetic Organic Chemistry, Japan

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.38, no.11, pp.1025-1036, 1980-11-01 (Released:2010-01-22)

参考文献数

38

被引用文献数

5 9

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Thienamycin, an exceptionally potent, broad spectrum β-lactam antibiotic, possesses a novel 1-carbapen-2-em structure. Total syntheses and synthetic approaches of thienamycin and its related compounds, which have been published before early in June of 1980, are summarized according to the manner for the formation of carbapenem and carbapenam ring systems.