有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
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74 巻, 4 号
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総説および総合論文
  • イソベンゾフランを用いた高次縮環芳香族化合物の合成
    羽村 季之
    2016 年 74 巻 4 号 p. 316-325
    発行日: 2016/04/01
    公開日: 2016/05/11
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.74.316
    ジャーナル 認証あり
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    Isobenzofurans are 10π electron systems with a quinoid structure, which make them useful intermediate for natural/unnatural product syntheses. Among various possibilities, [4+2] cycloaddition with dienophiles is a reliable method for the rapid construction of polycyclic structure. In this context, a one─pot synthetic method of 1,3─diarylisobenzofurans has been developed via sequential nucleophilic addition to 2─formylbenzoate. 1,3─Bis (arylethynyl)─isobenzofurans has also been accessible by nucleophilic addition of alkynyllithium to benzocyclobutenone and subsequent oxidative ring cleavage of the four─membered ring.  Based on these new synthetic approaches to various isobenzofurans, successive [4+2] cycloadditions of isobenzofuran with benzynes and/or epoxynaphthalenes were developed, allowing us for rapid construction of various highly condensed aromatic compounds. Moreover, as a potentially versatile method for the rapid, selective assembly of functionalized polycycles, we also exploited the synthetic equivalent of bis─isobenzofuran, i.e. diepoxyanthracene, which enabled the iterative generation of isobenzofuran and subsequent functionalization and/or introduction of the fused ring by trapping with dienophile.  The essential point of these integrated syntheses is isolability of isobenzofuran, which would provide great opportunities to use this potentially attractive molecules under various reaction conditions.
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  • アラインを用いた複素環化合物の合成
    大熊 健太郎
    2016 年 74 巻 4 号 p. 326-334
    発行日: 2016/04/01
    公開日: 2016/05/11
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.74.326
    ジャーナル 認証あり
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    Synthesis of nitrogen, oxygen, sulfur, and selenium containing heterocycles from aryne intermediates was reviewed. Reaction of (2-trimethylsilylphenyl)phenyliodonium triflate with thiobenzophenones in the presence of CsF gave the corresponding [4+2] cycloadducts, whereas reaction with thiopivalophenones afforded the [2+2] cycloadducts. Reaction of selones with benzyne produced from (2-trimethylsilyl)phenyl triflate also produced benzoselenetes. In the case of selenofenchone, initial cycloadduct further reacted with another molar of benzyne to give the corresponding selenoxanthene. Benzyne also reacted with ortho-substituted hydroxybenzoyl derivatives to afford the xanthene derivatives. Three component reaction involving benzyne, THF, and chloroform afforded phenyl ω-trichloroalkyl ethers via 1,3-oxonium zwitterion intermediates. Carbon-carbon single bond insertion of benzyne into β-diketones followed by intramolecular aldol reaction gave 4-substituted 2-naphthols regioselectively, which further oxidized by vanadium oxide to afford 4,4’,2,2’-binaphthols in good yields. This methodology would be applicable for the synthesis of biologically or pharmaceutically active products such as isocoumarins and benzodiazepines in one-pot operation.
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  • 生物活性含窒素複素環化合物の立体選択的合成法の開発：天然物合成ならびに有機触媒への応用研究
    名取 良浩, 今堀 龍志, 吉村 祐一
    2016 年 74 巻 4 号 p. 335-349
    発行日: 2016/04/01
    公開日: 2016/05/11
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.74.335
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    Iminosugars are biologically interesting compounds, since they can inhibit various glycosidases, and are considered as promising drug candidates, e.g, antidiabetes. We developed several methods for syntheses of various iminopyranose and iminofuranose derivatives. Our synthetic strategy was based on a combination of metathesis and asymmetric reaction. The first report regarding synthesis of (+)-isofagomine was based on ring-closing enyne metathesis and lipase-catalyzed kinetic resolution of allylic alcohols. The kinetic resolution was also applied to synthesis of various pipecolic acid derivatives, which were shown to act as effective organocatalysts for asymmetric Mannich reaction. As a second approach, iridium-catalyzed asymmetric allylic amination of allyl carbonate was used for the synthesis of 2-propylisofagomine. For the synthesis of polyhydroxylated pyrrolidines, we employed Pd-catalyzed allylic amination of butadiene monoxide developed by Trost and modified it. In the course of biological studies of synthetic compounds, we found that 1-C-butyl-L-arabino-iminofuranose (LAB) has potent inhibitory activities against α-glycosidases. Futhermore, we applied iridium-catalyzed allylic amination to the cyclization of allyl carbonate derivatives and found that the nosyl-protected amine could successfully cyclize to form a pyrrolidine ring in which the constructed sterogenic centers were controlled by the asymmetric catalyst. The method can be successfully applied to synthesis of (+)-bulgecinine and (+)-preussin.
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  • 生物活性縮環天然物の全合成におけるラジカル環化戦略
    好光 健彦
    2016 年 74 巻 4 号 p. 350-359
    発行日: 2016/04/01
    公開日: 2016/05/11
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.74.350
    ジャーナル 認証あり
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    The present article discusses our recent endeavors on natural product syntheses wherein radical reactions are strategically employed to access fused carbocycles. Particular emphasis is placed on the radical cyclizations that made it possible to establish the unique bond connectivity and functionalities of the target natural products. The radical chemistry-based approaches to platencin and clavilactone B are discussed here to show the utility of titanocene(III)-mediated epoxy enone cyclization, decarboxylative radical cyclization of an alkynyl carboxylic acid derivative with lead(IV) in 1,4-dioxane, and samarium(II)-mediated radical cyclization-fragmentation of an unsaturated keto ester, all of which serve as versatile means to elaborate the natural products.
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  • 光による分子活性化を利用した含ヘテロ多環系骨格構築手法の開発
    新井 則義, 大熊 毅
    2016 年 74 巻 4 号 p. 360-371
    発行日: 2016/04/01
    公開日: 2016/05/11
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.74.360
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    Novel methods for the construction of molecular frameworks were developed by means of photochemical activation of 5-membered heteroaromatics, including furans, thiophenes, thiazoles, and oxazoles. Intramolecular Diels-Alder-type cycloaddition reactions between furan and an unactivated alkene moiety were found to proceed in high yields in the presence of 9,10-dicyanoanthracene under UV irradiation to afford oxabicyclo[2.2.1]heptane derivatives with high stereoselectivity. Photoirradiation onto α-arylthiophene derivatives linked with an alkene moiety through a three-atom spacer gave unprecedented cyclobutene-fused perhydrothiapentalene-type compounds in high yields with high stereoselectivity. A photo-ene type cyclization of 2-aryloxazole derivatives linked with an alkene moiety through a three-atom spacer at the 5-position gave a range of functionalized spiro[4.4] cyclic compounds that included cyclopentane, tetrahydrofuran, and pyrrolidine moieties in moderate to high yields with excellent diastereoselectivity.
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