著者

大村 智

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.58, no.5, pp.392-393, 2000-05-01

参考文献数

5

著者

熊本 卓哉 石川 勉 大村 智

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.62, no.1, pp.49-58, 2004-01-01

参考文献数

39

被引用文献数

15

---

Kinamycin antibiotics, strongly active against gram-positive bacteria, were isolated from the culture broth of <I>Streptomyces murayamaensis</I>. Their structures were firstly determined to be a benzo [<I>b</I>] carbazoloquinone skeleton with <I>N</I>-cyanamide [N-C&equiv;N] moiety. After that, prekinamycin was isolated from the same organism as a biosynthetic precursor and the same 6-6-5-6 ring system was also proposed for the structure. But problems still remained on the determination of substituent pattern at <I>N</I>-cyanamide moiety by spectroscopic means. Recently, the structures of kinamycins and prekinamycin were revised to be a benzo [<I>b</I>] fluorene skeleton with diazoalkane moiety [C<SUP>-</SUP>-N<SUP>+</SUP>&equiv;N]. However, a synthetic compound with the revised structure for prekinamycin was found to be different from natural prekinamycin, instead an isomeric benzo [<I>a</I>] fluorene skeleton, a 6-5-6-6 ring system was proposed for the natural product, which was newly named as isoprekinamycin. Herein the chemistry of kinamycins and their related compounds with structural confusions is reviewed, especially focused on the history of structural determination and recent synthetic studies.

著者

砂塚 敏明 長光 亨 大村 智

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.56, no.6, pp.478-488, 1998-06-01

参考文献数

37

被引用文献数

2

---

The first total synthesis of the microbial a-pyrone meroterpenoid, (+) -pyripyropene A (1), acyl-CoA : cholesterol acyltransferase (ACAT) inhibitor, which is effective and concise convergent approach (14 steps, 9.3% overall yield), designed to afford easy access to both the natural products and a variety of analogs, has been achieved. The key step is the coupling reaction between a-pyronepyridine moiety (4) and the acid chloride of sesquiterpene moiety (3) in the presence of Lewis acid to construct ketone (2). The sesquiterpene moiety has been synthesized started from (+) -Wieland-Miescher ketons via stereoselective reductive formylation, palladium associated carbonylation, and allylic oxidation.<BR>(+) -Pyripyropene E (36) also has been synthesized from farnesyl acetate (9 steps, 9.6% overall yield). The convergent and stereoselective route exploited a biomimetic polyene cyclization as the key transformation.

著者

砂塚 敏明 長光 亨 大村 智

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.54, no.9, pp.740-751, 1996-09-01

参考文献数

48

被引用文献数

3

---

A total synthesis of the microbial metabolite (+) -lactacystin (1), the first non-protein neurotrophic agent, has been achieved in 11 steps (14% overall yield) from 2 (R), 3 (S) -3-hydroxyleucine. The key steps in the elaboration of the lactam moiety include the stereoselective hydroxymethylation of oxazoline and an asymmetric allylboration of the aldehyde which introduce the hydroxyl and methyl substituents at C (6) and C (7).<BR>This new asymmetric approach furnished four stereoisomers of 3-hydroxyleucine as required starting material in high overall yield and enantiomeric purity.<BR>Furthermore, the construction of several active analogs and the structure-activity relationships of lactacystin are also described.

著者

溝口 玄樹

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.75, no.3, pp.253-254, 2017

被引用文献数

3

---

<p>Polyoxygenated steroids cardenolides, typified by ouabagenin, possess a broad spectrum of biological activity such as inotropic activity. Due to their unique structure, including unusual <i>cis</i>-fused A/B- and C/D ring junction, and a number of β-configured oxygenated functional group, they have been an attractive target in chemical synthesis. In this review, recent developments in the practical synthetic strategies toward these cardenolides are described.</p>

著者

ウイルシヤー イーアール

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.12, no.4, pp.144-150, 1954

著者

浅原 時泰

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.72, no.6, pp.728-729, 2014-06-01 (Released:2014-07-16)

参考文献数

12

---

Nitroso compounds have drawn much attention of synthetic organic and biological chemists because of their usefulness as synthetic intermediate as well as interesting bioactivity. Here, a recent report about the simple and selective preparative method for nitrosoarenes using nitrosonium tetrafluoroborate is described. It provides versatile nitrosoarenes including heteroarenes which are not easily prepared by alternative method.

著者

吉田 泰志

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.76, no.1, pp.55-56, 2018-01-01 (Released:2018-01-16)

参考文献数

15

被引用文献数

1

---

Regio- and stereoselective synthesis of organoboron compounds has great importance due to their wide applicability and high stereospecificity in many transformations such as Suzuki-Miyaura cross coupling reaction. Generally, hydroboration of unactivated terminal alkenes proceeds in anti-Markovnikov selective manner to produce linear products. In this short review, recent examples of catalytic Markovnikov hydroboration of unactivated terminal alkenes, and its application to asymmetric synthesis are described.

著者

荒井 孝義

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.76, no.1, pp.3-10, 2018-01-01 (Released:2018-01-16)

参考文献数

89

---

A chiral N,N,N-terdentate bis(imidazolidine)pyridine (PyBidine) has showed remarkable ligand acceleration effects in various metal catalyzed asymmetric reactions. For an example, PyBidine-Cu(OTf)2 catalyzed a highly endo-selective [3+2] cycloaddition of nitroalkenes with imino esters. X-ray crystallographic analysis of the PyBidine-Cu(OTf)2 complex and DFT calculations suggest that an intermediary generated Cu-enolate of the imino ester reacts with nitroalkenes, which are activated by NH-proton of imidazolidine ligand. Based on the intelligent role of imidazolidine, a new chiral imidazolidine-containing NCN palladium pincer complex (tBu-PhBidine-PdX) was prepared by a ligand introduction route. The neutral tBu-PhBidine-PdCl complex demonstrated significant catalytic activity for the reaction of nitroalkenes with malononitrile to give the products in good yields with high enantioselectivities. On the contrary, the cationic chiral imidazolidine-containing tBu-PhBidine-PdOTf catalyst promoted the nucleophilic addition of unprotected indoles to N-Boc imines. Using sulfinyl amines as the N-Boc imine precursors, the combined use of catalyst with K2CO3 activated the N-H-free indoles to give chiral 3-indolyl methanamines with up to 98% ee. Compared with conventional acid-catalyzed Friedel-Crafts reactions, this reaction proceeding under mildly basic conditions shows advantages for the use of acid-sensitive substrates. Furthermore, chiral bis(imidazolidine)-containing PhBidine-Rhodium complexes (PhBidine-RhX2 and tBu-PhBidine-RhX2) were prepared by a C-H insertion method. The tBu-PhBidine-Rh(OAc)2 smoothly catalyzed an asymmetric Mannich reaction of malononitrile with N-Boc imines to give products, which are useful for the synthesis of chiral α-amino acids.

著者

福山 勝

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.23, no.8, pp.700-712, 1965-08-01 (Released:2011-03-01)

参考文献数

77

著者

中山 重蔵

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.28, no.2, pp.132-143, 1970-02-01 (Released:2010-01-28)

参考文献数

62

被引用文献数

1 4

著者

藤野 政彦

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.52, no.5, pp.439-444, 1994-05-01 (Released:2009-11-16)

参考文献数

6

被引用文献数

1

---

Biologically active peptide have potential therapeutic applications in the treatment of diseases caused by peptide deficiency. However, there are only a few peptide drugs, Elcitonin (a calcitonin derivatives for osteoporosis, Asahikasei), Hirutonin (TRH tartrate for prolonged disturbance of consciousness, Takeda) and Leuplin (a highly potent LH-RH derivative for prostate cancer/endometriosis, Takeda) There are two serious drawbacks to using peptide derivatives as drugs : their poor oral bioavailability and their short duration of activity. Although the latter can be overcome by studing various derivatives, the development of orally active peptide derivatives is almost impossible. I would like to describe briefly the process of the research and development of “Leuplin Depot”, once-a-month depot type formulation of super agonist of LH-RH.

著者

松田 知子 原田 忠夫 中村 薫

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.59, no.7, pp.659-669, 2001-07-01 (Released:2010-01-22)

参考文献数

17

被引用文献数

3 4

---

Biocatalyst has been attracted increasing attention for asymmetric synthesis due to the high enantioselectivities and environmentally friendliness. We have been developing methods using a fungus, Geotrichum candidum, which has many enzymes catalyzing the enantioselective oxidation and reduction reactions of non-natural substrates. These enzymes in the resting or dried cells were used in an organic solvent, supercritical carbon dioxide, or aqueous media for oxidation, reduction or deracemization reactions. The usefulness of these methods was also demonstrated in the preparation, on a multi-gram scale, of optically pure alcohols.The effect of fluorine substituents on the enantioselectivity of the reduction using the dried cell was also investigated thoroughly, and it was found that the reduction of trifluoromethyl ketones affords (S) -trifluoromethyl carbinols in excellent ee, whereas the reduction of methyl ketones gives the corresponding alcohols of the opposite configuration in excellent ee. The enzymes in the cells were separated to investigate the origin of different enantioselectivities between the methyl and trifluoromethyl ketones.

著者

平川 芳彦

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.35, no.5, pp.325-331, 1977-05-01 (Released:2009-11-13)

参考文献数

10

---

Sulfur (S) is an element of 15th largely existed in earth's crust, 10th in universe, and 7th in human body. S circulates the environmental sphere in various chemical forms, but SO2 in atmosphere is largely responsible by human burning of S contained fuels and minerals. Underground resources of S and production type of S differ country by country. S content in crude oil varies ranging from less than 0.1% to more than 5% in every oilfield. Large S content unexpected from biological source theory of oil origin might be explained by that melted mineral origin elementary S in underground has met and dissolved into highly aromatic or naphthenic fractions of crude oil and secondarily converted to S compounds. Though supply of S as fertilizer to fields has been decreased, but SO2 has played an important role of natural supply of S to the earth, especially in highly populated metropolitan areas.

著者

長谷川 元 三浦 剛毅 渡谷 哲朗 洪 南基

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.56, no.9, pp.773-780, 1998-09-01 (Released:2009-11-16)

参考文献数

52

被引用文献数

1 1

---

To date, the resolution of racemic mixture via diastereomeric salt formation has been the most commonly used industrial technique.We have synthesized and applied new resolving agents for industrial application. Practical approach to the developments is as follows. Optically active 2-phenoxypropionic acid and tartranilic acid are readily employed for the resolution of bases, and 1-benzylamino-3-phenoxy-2-propanol for the resolution of acids.

著者

大饗 茂 北尾 弟次郎

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.19, no.12, pp.880-899, 1961-12-01 (Released:2010-10-20)

参考文献数

117

被引用文献数

2

著者

北原 武 宮下 晃

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.46, no.2, pp.179-179, 1988-02-01 (Released:2009-11-13)

著者

稲木 良昭

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.51, no.3, pp.188-202, 1993-03-01 (Released:2009-11-16)

参考文献数

31

被引用文献数

6 7

---

Pyrimidine derivatives were found to be applicable to photoresists for microelectronics. This paper deals with synthesis and photochemistry of pyrimidine derivatives, and application to photoresists. Intermolecular photodimerization of pyrimidine bases in the side chains of various polymeric and dimeric compounds upon irradiation of UV light (270 nm) led to photocrosslinking of the polymer chains or photopolymerization of the dimeric compounds. These materials can be used as deep-UV negative type photoresists. On the other hand, the polymers containing thymine photodimers in the main chain underwent dissociation of the thymine photodimers upon irradiation to UV light (250 nm), leading to breakage of the polymer chains. These polymers could be used as positive type photoresists and high resolution (0.3μm) was demonstrated. Tautomerism of pyrimidine was also applied to a chemical amplification photoresist system. Polymers containing 2, 4-dialkoxypyrimidine derivatives that is an enol form of uracil were high sensitive deep-UV, and EB chemical amplification resists.

著者

青木 貞己

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.7, no.1-2, pp.18-20, 1949-04-01 (Released:2010-10-20)

著者

井上 宗宣

出版者

社団法人 有機合成化学協会

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.75, no.4, pp.310-319, 2017-04-01 (Released:2017-04-28)

参考文献数

76

---

The introduction of fluorine-containing carbon functional groups into organic compounds is one of the key processes to synthesize biological valuable organofluorine compounds. While the reaction of organolithium, magnesium and zinc reagents with appropriate carbon electrophiles is reliable method to form carbon-carbon bonds, there were few reports concerning the reaction of these organometallic reagents with electrophilic fluoroalkylating reagents. Recently, we have developed several fluoroalkylations using these organometallic reagents and electrophilic fluoroalkylating reagents. In this paper, we account the fluoroalkylation of aromatic lithium, magnesium, and zinc reagents including our developed bromodifluoromethylation of aryl Grignard reagents with CF2Br2 and dibromofluoromethylation of aryl Grignard reagents with CF2Br2 in the presence of LiBr. In addition, the (ethoxycarbonyl)difluoromethylation of arylzinc reagents with ethyl bromodifluoroacetate in the presence of cobalt catalysts is also discussed.