有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
62 巻, 6 号
選択された号の論文の8件中1~8を表示しています
  • 松尾 淳一
    2004 年 62 巻 6 号 p. 574-583
    発行日: 2004/06/01
    公開日: 2009/11/13
    ジャーナル フリー
    Various alcohols are smoothly oxidized to the corresponding carbonyl compounds by using a stoichiometric amount of a new oxidant, N-tert-butylbenzenesulfinimidoyl chloride (1), in the coexistence of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU). A new catalytic method mediated by a catalytic amount of 1 was further developed in order to solve the difficulties on purification of formed carbonyl compounds after this stoichiometric oxidation. That is, catalytic oxidation of various alcohols is efficiently performed by using a catalytic amount of N-tert-butylbenzenesulfenamide (2) and a stoichiometric amount of N-chlorosuccinimide (NCS). The catalytic oxidation is more useful than the above-mentioned stoichiometric one because of its wide applicability and efficiency. The new oxidant 1 efficiently dehydrogenates organic compounds other than alcohols. For example, ketones are smoothly dehydrogenated to α, β-unsaturated ketones at -78°Cin a one-pot manner by the reaction of lithium enolates of ketones and 1. Further, a variety of amines and hydroxylamines are also oxidized to the corresponding imines and nitrones, respectively, by using 1 and DBU under very mild conditions.
  • 生合成経路の解明と新たなラジカル消去機構の発見
    阿部 尚樹, 廣田 陽
    2004 年 62 巻 6 号 p. 584-597
    発行日: 2004/06/01
    公開日: 2009/11/13
    ジャーナル フリー
    In the course of our screening to find 1, 1-diphenyl-2-picrylhydrazyl (DPPH) radical scavengers, we isolated eleven sorbicillin-related compounds, including seven novel compounds, from the fermentation broth of Trichoderma sp. USF-2690. The “bisorbicillinoids” was recently defined by Nicolaou as the term used to designate a group composed of dimeric sorbicillin-related natural products, on which their diverse structures and interesting biological activities were reported by several groups. A few research groups had described biogenesis of bisorbicillinoids, and consequently some distinguishable biosynthetic routes had been presented. Herein we report (1) finding of a functional quinol, sorbicillinol (12), postulated as a key compound in bisorbicillinoids biosynthesis for a long time, (2) evidence for the biosynthetic pathway, via sorbicillinol (12), of sorbicillin (11), bisorbicillinol (1), bisorbibetanone (9), bisorbicillinolide (3), and bisvertinolone (8), and (3) study on a radical scavenging mechanism of bisorbicillinol (1).
  • α-ヒドロキシメチルエノンの不斉骨格転位反応
    三上 幸一, 松本 祥治, 田中 悟史
    2004 年 62 巻 6 号 p. 598-606
    発行日: 2004/06/01
    公開日: 2009/11/13
    ジャーナル フリー
    Asymmetric photochemical synthesis has still remained as the frontier in science and technology, for which circular polarized light and chiral sensitizers have been employed. We report the photochemical carbon skeletal reorganization of the α-hydroxymethylenone, involving the Cs symmetric dihydroxytrimethylenemethane ((OH)2-TMM) as a common intermediate. Asymmetric desymmetrization of the Cs symmetric (OH)2-TMM intermediates by matched C2 symmetric chiral controllers with a chiral supercage provides an asymmetric route to the photochemical synthesis of 1, 4-dicarbonyl compounds of synthetic use for cyclopentanoids and 5-membered heterocycles. The enantiospecific carbon skeletal rearrangement through triple binding with C2 symmetric chiral controllers, diphenylethylenediamine (DPEN) and a chiral supercage, γ-CD is thus highlighted.
  • 船曳 一正
    2004 年 62 巻 6 号 p. 607-615
    発行日: 2004/06/01
    公開日: 2009/11/13
    ジャーナル フリー
    This article presents novel efficient and stereoselective synthesis of fluorine-containing organic compounds by using new reactions of enol tosylates with polyfluoromethyl group as well as fluorine atom. β-Fluoro-β-polyfluoromethyl-α- (tosyloxy) vinyllithiums, generated by the reaction of polyfluoropropyl p-toluenesulfonates or β-fluoro-β-polyfluoromethyl-enol tosylates with n-butyllithium, readily react with a variety of electrophiles to give the corresponding α-substituted β-fluoro-β-polyfluoromethyl-enol tosylates in good yields. Obtained fluorinated enol tosylates participate nicely in nucleophilic reactions with various nitrogen, sulfur, oxygen, and carbon nucleophiles, as well as other reactions. The present reactions provide new entries to various organofluorine compounds based on the selective transformation of enol tosylates by tuning with polyfluoromethyl group or fluorine atoms.
  • 白川 英二
    2004 年 62 巻 6 号 p. 616-628
    発行日: 2004/06/01
    公開日: 2009/11/13
    ジャーナル フリー
    Carbometalation of alkynes produces cis-substituted alkenylmetals and is an extremely useful method for a stereoselective olefin synthesis, since the resulting alkenylmetals can be transformed further to variously substituted ethenes. We have been disclosing diverse types of transition metal-catalyzed carbostannylations of alkynes, 1, 3-dienes and 1, 2-dienes, featuring much higher chemoselectivity compared with the previously reported carbometalations with more nucleophilic organometallic compounds. Alkynyl- and allylstannylations of alkynes were catalyzed by a palladium complex with or without iminophosphine ligand, whereas nickel complexes catalyzed the addition of alkynyl-, allyl- and acylstannanes. Nickel catalysts were found to be effective also for acyland alkynylstannylations of 1, 3- and 1, 2-dienes. The carbostannylation of alkynes in the presence of a palladium-diimine complex was accompanied by dimerization of alkynes, where the carbon-tin bond of alkynyl-, alkenyl-, allyl-, aryl- and heteroarylstannanes accepted insertion of two molecules of an alkyne.
  • 田所 誠
    2004 年 62 巻 6 号 p. 629-640
    発行日: 2004/06/01
    公開日: 2009/11/13
    ジャーナル フリー
    Manipulation of molecular crystals formed from self-organization is one of important methods to develop the new molecular functional materials. We have been looking upon in particular mutual cohesive interactions of hydrogen bonding and metal coordination as one of useful tools to construct the preprogramming super-structures. In this study, five controlled super-structures of a one-dimensional linear chain, a zig-zag ribbon, right-handed and left-handed helices, and a two-dimensional honeycomb sheet are newly created by using the neutral metal complexes with some 2, 2'-biimidazolate mono-anions.
  • 阿部 尚樹, 田所 誠
    2004 年 62 巻 6 号 p. 641
    発行日: 2004/06/01
    公開日: 2009/11/13
    ジャーナル フリー
  • 第2回 有機合成化学協会中国四国支部
    2004 年 62 巻 6 号 p. 642-651
    発行日: 2004/06/01
    公開日: 2009/11/13
    ジャーナル フリー
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