著者

宮浦 憲夫 鈴木 章

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.46, no.9, pp.848-860, 1988

被引用文献数

1 13

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A general and convenient method for the stereo-and regioselective synthesis of conjugated alkadienes, alkenynes, arylated alkenes, and heterobiaryls is described. The reaction of (<I>E</I>) -or (<I>Z</I>) -1-alkenylboronates obtainable by hydroboration, with either (<I>E</I>) -or (<I>Z</I>) -1-alkenyl halides in the presence of a catalytic amount of tetrakis (triphenylphosphine) palladium and bases such as sodium alkoxides gives the corresponding (<I>E</I>, <I>E</I>) -, (<I>E</I>, <I>Z</I>) - (<I>Z</I>, <I>E</I>) -and (<I>Z</I>, <I>Z</I>) -alkadienes stereo-and regioselectively, while retaining the configuration of both the starting alkenylboronates and haloalkenes The similar reactions of (<I>E</I>) -and (<I>Z</I>) -1-alkenylboronates with 1-alkynyl, aryl, allylic, and benzylic halides also provide the corresponding couplig products stereosoelectively. The versatility of this method has been demonstrated by the synthesis of some natural products bearing conjugated alkadiene structures. The reaction of arylboronic acids with aryl halides to give unsymmetrical biaryls is also presented. A mechanism of this cross-coupling reaction, which involves the transmetallation between a 1-alkenylborane and an alkoxopalladium (II) complex generated through the metathetical displacement of a halogen atom of RPd (II) X with sodium alkoxide, is proposed.

著者

下山 敦史

出版者

公益社団法人 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.3, pp.303-304, 2014-03-01 (Released:2014-04-21)

参考文献数

11

---

Investigating the function of native biomolecules is an important but challenging task due to the highly complex nature of biological systems. To understand complex biological systems in terms of simple biomolecular interactions, organic chemists have developed many bioorthogonal reactions over the past few years. These bioorthogonal reactions have been applied for the efficient construction of functionalized biomolecules. In this mini review, the development and the applications of such bioorthogonal reactions are described.

著者

西沢 麦夫

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.51, no.7, pp.631-640, 1993-07-01 (Released:2010-01-28)

参考文献数

51

被引用文献数

1 2

---

Significant attentions have been focused on the inclusion chemistry of cyclodextrins and the related compounds and synthetic studies of cyclooligosaccharides have been tarring out intensively. For example, Ogawa and coworkers reported the total synthesis of cyclodextrins and a manno isomer of cyclodextrins by means of phenylselenyl triflate promoted cycloglycosylations. Synthesis of 1-3β linked cycloglucohexaose was reported by Collins' group. Modifications of α-cyclodextrin into trimethyl, 1, 3-anhydro, and a chimera analog have also reported recently. However, cyclooligosaccharide available today is only limited to D series. As we have developed a novel thermal glycosylation procedure, which can be applied to rhamnosylation with high α-selectivity, we designed the synthesis of cyclo-L-rhamnohexaose (40), the first cyclooligosaccharide of L series. On the basis of the area where the compound has been prepared, this compound was named α-cycloawaodorin, which would open a new dimension of the inclusion chemistry.

著者

福永 隼也

出版者

公益社団法人 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.81, no.6, pp.607-608, 2023-06-01 (Released:2023-06-07)

参考文献数

7

---

Aromaticity is an important concept that controls the stability, electronic property and reactivity of π-conjugated compounds. The conventional understanding of aromaticity, however, often fails to explain the behavior of compounds with highly complicated networks. This review highlights the recent development of syntheses of 3D π-conjugated macrocycles and discussions about aromaticity in 3D π-conjugated systems.

著者

吉田 善一 小田 良平

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.9, no.11, pp.230-235, 1951-11-30 (Released:2010-10-20)

参考文献数

70

被引用文献数

2 2

著者

吉田 潤一

出版者

公益社団法人 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.4, pp.373-375, 2018-04-01 (Released:2018-04-06)

参考文献数

15

著者

榊原 陽太 伊丹 健一郎 村上 慧

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.81, no.11, pp.1050-1061, 2023-11-01 (Released:2023-11-10)

参考文献数

56

被引用文献数

1

---

Carboxylic acids are one of the most important functional groups found in various feedstocks. Their significance lies in their pivotal role as key intermediates in selective transformations during organic synthesis. Despite the existence of various decarboxylative transformation reactions such as Kolbe dimerization, these methods still exhibit certain limitations that present opportunities for further improvement. In this account, we present our recent studies on the application of photocatalytic decarboxylative transformation that allows the divergent transformation of carboxylic acids.

著者

米沢 正次

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.30, no.9, pp.823-831, 1972-09-01 (Released:2009-11-13)

参考文献数

77

被引用文献数

3 5

著者

張本 尚 石垣 侑祐

出版者

公益社団法人 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.81, no.10, pp.963-977, 2023-10-01 (Released:2023-10-05)

参考文献数

40

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In recent years, near-infrared (NIR) dyes, exhibiting absorption in the NIR region (750-2500 nm), has been applied to various optical applications such as security marking, photovoltaic cells and chemotherapy of deep tissues in vivo. Electrochromic systems capable of switching NIR absorption are attractive from the viewpoint of applications for material and life science, and thus several examples have been reported to date. The development of organic-based materials is needed to reduce the environmental impact and improve biocompatibility. However, since the redox states of organic NIR dyes are generally unstable, the switching of NIR absorption based on quantitative redox interconversion is still a challenging issue regarding reversibility and durability during their interconversion. To construct organic electrochromic systems capable of ON/OFF switching of NIR-absorbing properties, we have focused on the non-aromatic π-conjugated para-quinodimethane (p-QD) skeleton. Herein, we have shown several studies on the synthesis and functional control of NIR electrochromic molecules based on redox-active p-QD scaffolds. We have elucidated the spectroscopic and electrochemical properties of various arylated quinodimethane derivatives and demonstrated that p-QD building blocks can be versatile components for the development of NIR switchable organic electrochromic systems.

著者

谷 洋介 小村 真央

出版者

公益社団法人 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.81, no.5, pp.492-500, 2023-05-01 (Released:2023-05-10)

参考文献数

42

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Phosphorescence is a unique luminescence property with a number of advantages that are complementary to those of fluorescence. However, achieving efficient room-temperature phosphorescence (RTP) using metal-free organic molecules is a challenging task owing to the spin-forbidden nature of phosphorescence. Extensive research in the last decade has revealed that decent RTP can be obtained from organic crystals based on the suppression of nonradiative decay. Nonetheless, once the rigid crystalline lattice is destroyed by applying mechanical stimuli, such RTP often disappears. We have recently developed heteroaromatic 1,2-diketones as a novel scaffold of organic RTP. Unlike conventional phosphors, the diketones exhibit efficient RTP in various noncrystalline states/environments. This article describes the RTP of halogenated thienyl diketone derivatives, focusing on their response to mechanical stimuli and the multiple and indispensable roles of halogens therein.

著者

谷本 裕樹

出版者

公益社団法人 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.80, no.12, pp.1100-1112, 2022-12-01 (Released:2022-12-06)

参考文献数

43

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Organic azides are well-known for the synthetic organic reactions by their energetic characteristics and the click functionality connecting two components. Especially in click chemistry, the azido groups as 1,3-dipolar play a key role in chemical biology. On the other hand, azido groups can also work as nucleophiles possessing diazonium leaving groups and as electrophiles, but the low reactivity has avoided their use. Herein, we disclose our synthetic achievements in the non-1,3-dipolar use of organic azides. As nucleophiles, the organic azides with allyl/propargyl cations and sulfonium ions gave the appropriate products, including C-C bond migration. We also demonstrated that the intramolecular hydrogen bonding interaction promoted the electrophilicity and suppressed the nucleophilicity of the azides to achieve site-selective conjugation. Furthermore, β-elimination followed by condensation converted the azido groups at the carbonyl α-position to the different click functional groups. This site-selective azido group conversion enabled the undistinguishable triazide molecule to the distinguishable triple-click scaffold compound possessing three different click groups.

著者

和佐 雅幸 Ahmet Yesilcimen

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.79, no.11, pp.1065-1072, 2021-11-01 (Released:2021-11-10)

参考文献数

182

被引用文献数

2

---

Cooperative actions of two or more Lewis acid and/or Lewis base catalysts can be exploited to promote enantioselective transformations that are not readily achieved by a single catalyst system. Nonetheless, undesirable acid-base complexation which occurs in a reaction mixture containing the catalysts, substrates, and products often results in poor reaction efficiency and a contrived substrate scope. In this article, we highlight our development of multi-catalyst systems that facilitate enantioselective transformations of otherwise unreactive C-H bonds contained in various carbonyl compounds and N-alkylamines while overcoming the formation of inert Lewis adducts. Such methods were achieved through the identification of catalyst/substrate combinations that form frustrated Lewis pairs (FLPs), namely, highly active acids and bases whose mutual quenching is precluded due to steric and electronic factors.

著者

山田 静之 木越 英夫

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.53, no.1, pp.13-21, 1995-01-01 (Released:2009-11-16)

参考文献数

22

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Synthetic studies on the bracken ultimate carcinogen (3) and its artificial analogues (32, 33) are described. The synthesis of (-) -ptaquilosin (2) the aglycon of a potent carcinogen ptaquiloside (1) from bracken and its (+) - enantiomer (ent- 2) was achieved starting with (+) -dimenthyl (1R, 2R) -cyclopentane-1, 2-dicarboxylate. Dehydration of ptaquilosin (2) under weakly basic conditions led to the ultimate carcinogen (3). DNA cleaving activities of both enantiomers (3) were compared, the one (3) derived from natural (-) -ptaquilosin (2) being more efficient. Reactivities of the ultimate carcinogen (3) toward DNA are described. DNA was shown to be alkylated at the particular sites of purine bases and to undergo cleavage. The molecular mechanism of DNA cleavage with the ultimate carcinogen (3) was disclosed using deoxytetranucleotide d (GTAC) as a model DNA substrate.

著者

下川 淳 福山 透

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.11, pp.1115-1124, 2017-11-01 (Released:2017-11-09)

参考文献数

174

被引用文献数

1

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Five total syntheses of heteropolycyclic natural products, namely hyalodendrin, tryprostatins, spirotryprostatin A, the core of the stemofoline alkaloids, and hinckdentine A, are outlined. These syntheses share common characteristics; the sequences of transformations are facilitated through the development of new synthetic reactions and the discoveries of unknown molecular reactivities. Brief descriptions of new reactions, the mechanistic details of key transformations, and the resulting shortcuts and efficiencies made possible in relation to the overall “picture” of these total syntheses are described.

著者

千藤 三千造

出版者

公益社団法人 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.14, no.7, pp.472-475, 1956-07-01 (Released:2010-10-20)

著者

安川 知宏 久田 智也 中島 華子 増田 隆介 北之園 拓 山下 恭弘 小林 修

出版者

公益社団法人 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.81, no.4, pp.353-361, 2023-04-01 (Released:2023-04-08)

参考文献数

57

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Molecular sieves are type A zeolites with specific sized pores and are commonly used in organic synthesis to capture small molecules such as water. In addition to their trapping effect, they also have acidic and basic active sites and are used as solid acid-base catalysts. Usually, heat-drying treatments are performed prior to use, but the heat treatment methods, such as microwave ovens or heat guns, are not standardized, which could cause problems in reproducibility of reactions. Particularly, for reactions requiring acid/base sites of molecular sieves, these treatment methods are considered more sensitive because the structure of the active sites changes upon heating. In this article, we propose new methods of activation when using molecular sieves and their application to continuous-flow reactions.

著者

柴田 勝太郎

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.14, no.2, pp.75-79, 1956 (Released:2010-10-20)

被引用文献数

1 1

著者

四方田 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.53, no.10, pp.918-919, 1995 (Released:2009-11-16)

著者

上原 忠夫 齋藤 研一 山本 嘉則

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.47, no.4, pp.321-329, 1989-04-01 (Released:2010-01-22)

参考文献数

79

被引用文献数

2 3

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High-pressure technique is a practical method for laboratory organic synthesis since simple equipment has become available in this decade. Pressure accelerates reactions if their values of 'the volume of activation' are negative, such as cycloaddition reactions and reactions through dipolar transition states. Especially, this technique is useful to drive reactions with steric hindrance. In this article are reviewed recent developments of substitution reactions, addition reactions to a carbonyl group, conjugated addition reactions, Deils-Alder reactions, 1, 4-cycloaddition reactions, other pericyclic reactions, and organometallic reactions since 1985.

著者

石垣 侑祐

出版者

公益社団法人 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.79, no.4, pp.290-299, 2021-04-01 (Released:2021-04-07)

参考文献数

35

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The carbon-carbon covalent bond is one of the most basic concept in organic chemistry. Bond length, bond angle, and torsion angle among carbon atoms are nearly constant on the basis of the bond order and hybrid orbitals. On the other hand, highly strained hydrocarbons such as sterically-congested and/or curved polycyclic aromatic hydrocarbons have attracted much attention with regard to their characteristic features. Regarding the C-C single bond, whose standard length is 1.54 Å, several attempts have been made to elongate the C-C single bond to gain new insight into the chemical bond and understand what happens at the limits of a bond. In contrast to the standard C=C double bond with planarity, the overcrowded ethylenes (OCEs) with bulky substituents can adopt anti-folded, syn-folded and/or twisted forms due to the steric hindrance around the central C=C double bond, and thus many OCEs exhibit photo- and thermochromic behavior upon exposure to external stimuli. Herein, we focus on redox-active hydrocarbons with two dibenzocycloheptatriene units, where unprecedented flexible C-C bonds based on extremely elongated C-C single bonds and control of HOMO levels were demonstrated. Thus, these highly strained hydrocarbons could be promising candidates for the development of functional materials.