Silver(I) ion-catalyzed rearrangement of 3,5-dehydronoriceane (pentacyclo(5.3.1.02,6.03,5.04,9)undecane). Empirical force-field calculations and behavior of 3-noricyl (tetracyclo(5.3.1.02,6.04,9)undec-3-yl) cation.

スポンサーリンク

概要

• 論文の詳細を見る

• Treatment of 3,5-dehydronoriceane (<B>1</B>) with a catalytic amount of silver tetrafluoroborate results in a novel skeletal rearrangement to afford tetracyclo[5.3.1.0<SUP>2,6</SUP>.0<SUP>3,9</SUP>]undec-4-ene (2,4-ethenonoradamantane) (<B>5</B>) in 85% yield. Empirical force-filed calculations suggest that there is no substantial difference in strain energies between <B>1</B> and bicyclo[2.1.0]pentane which is inert toward silver(I) ion. Acetolysis of <I>endo</I>-3-noricyl (<I>endo</I>-tetracyclo[5.3.1.0<SUP>2,6</SUP>.0<SUP>4,9</SUP>]undec-3-yl) tosylate (<B>7</B>) gives <I>exo</I>-3-acetoxynoriceane (<I>exo</I>-3-acetoxytetracyclo[5.3.1.0<SUP>2,6</SUP>.0<SUP>4,9</SUP>]undecane) (<B>11</B>), <I>exo</I>-4-acetoxytetracyclo[5.3.1.0<SUP>2,6</SUP>.0<SUP>3,9</SUP>]undecane (<B>12</B>), and <B>5</B> in a ratio of 36:42:22. Similar acetolysis of the <I>exo</I>-isomer of <B>7</B> gives the same products but in a different ratio (<B>11:12:5</B>=9:47:44). A stepwise carbocation mechanism is proposed for the above mentioned silver(I) ion-catalyzed rearrangement.

• 公益社団法人 日本化学会の論文

著者

• Osawa Eiji

  Department Of Chemistry Faculty Of Science Hokkaido University

• Kawanisi Mituyosi

  Department of Industrial Chemistry, Faculty of Engineering, Kyoto University

• Katsushima Takeo

  Department of Industrial Chemistry, Faculty of Engineering, Kyoto University

• Yamaguchi Ryohei

  Department of Applied Chemistry, Faculty of Engineering, Yokohama National University

• Kawanisi Mituyosi

  Department of Industrial Chemistry, Faculty of Engineering Kyoto University

関連論文

• Pd4 REFINEMENET OF MOLECULAR MECHANICS PARAMETERS : XV. ESTER AND ETHER GROUPS
• An Efficient Triple Allylation of 1,3,5-Triazine by Means of Tin Regent. Facile Synthesis of syn,syn-2,4,6-Trifunctionalized 1,3,5-Triazacyclohexanes
• Conformational Analysis of Curdione and Neocurdione(Organic,Chemical)
• Pb1 SHAPE ANALYSIS OF SERRICORNIN, THE SEX PHEROMONE PRODUCED BY FEMALE CIGARETTE BEETLE (LASIODERMA SERRICORNE F.)
• CLd3 APPLICATION OF MOLECULAR MECHANICS TO NATURAL PRODUCT CHEMISTRY
• Highly regioselective .ALPHA.-addition of alkynyl and alkenyl Grignard reagents to 1-alkoxycarbonylpyridinium salts and its application to synthesis of 1-azabicycloalkanes and (.+-.)-solenopsin A.
• Formation of diorganostannylenes. I. Photolytic reaction of dibutyltin with organic halides.
• The reaction of anhydrochloralurethanes with ketene acetals.
• Cyclic Diacylcarbene Generated from Iodonium Ylides and Diazodiketones
• Synthesis of 2,11-dehydrohomoadamantane (tetracyclo[5.3.1.02,4.03,9]undecane) and 2,11-dehydrohomoadamant-4-ene (tetracyclo[5.3.1.02,4.03,9]undec-5-ene).
• Diels-Alder Reaction of "Anhydrochloral-urethane" with 1,3-Dienes
• The Photo-induced Addition of Acetic Acid to Cyclohexene Derivatives
• The Synthesis of Coenzyme Q
• Silver(I) ion-catalyzed rearrangement of 3,5-dehydronoriceane (pentacyclo(5.3.1.02,6.03,5.04,9)undecane). Empirical force-field calculations and behavior of 3-noricyl (tetracyclo(5.3.1.02,6.04,9)undec-3-yl) cation.
• The Synthesis of 2,4-Dehydrohomoadamantane
• The Reaction of 7-Methylenebicyclo[3.3.1]nonan-3-one and Bicyclo-[3.3.1]nonane-3,7-dione with Several Nucleophiles
• The ESR Spectra of the Anthanthrene and Binaphthylene Dioxide Cation-radicals
• Lead tetraacetate oxidation of humulene and conformational analysis of the produced humulatrienediols.
• Photochemical Reactions of Diphenylacetylene with Enaminoesters
• The Reactions of Several Carbonyl Compounds with Hexamethylphosphoric Triamide
• Diorganostannylenes. II. Photolytic reaction of diphenyltin with alkyl halides.
• The Reaction of Alcohols with Hexamethylphosphoric Triamide
• Halogen Migration of 2,2-Dihaloadamantane Induced by Aluminum Halides
• Synthesis of 2,5-dehydrohomoadamantane (tetracyclo[5.3.1.02,5.03,9]undecane) from 2,4-dehydrohomoadamantane (tetracyclo[5.3.1.03,5.04,9]undecane).
• Convenient and improved synthesis of tricarbonyl(1,2-dihydropyridine)iron complex.
• Synthesis of 3-mono- and 3,5-difunctionalized noriceanes (tetracyclo(5.3.1.02,6.04,9)undecanes) via oxymetallation of 3,5-dehydronoriceane (pentacyclo(5.3.1.02,6.03,5.04,9)undecane). Oxidation of bicyclo(2.1.0)pentane system by mercury(II), thallium(III),
• Double Diels-Alder reactions of coumalic acid with 1,3-dienes.
• Halogenation of 3,5-dehydronoriceane (pentacyclo(5.3.1.02,6.03,5.04,9)undecane. Front side attack on the bicyclo(2.1.0)pentane system by halonium ion and corner side attack by halogen radical.
• Stereoselective syntheses of 3-acetyl-1,2-dimethyl-1-cyclopentanols. Syntheses of dl-plinols A,B, and C.
• Photochemistry of Non-enolizable β-Diketones Containing Cyclopropane Ring in Conjugation
• Reduction of 7-Methylenebicyclo[3.3.1]nonan-3-one and Related Compounds: Structural Investigation of the Products
• A novel synthesis of .DELTA.-amino acid derivatives.
• Synthesis of 4-methyl-1,2-oxathiin 2,2-dioxide.
• Noriceane (tetracyclo(5.3.1.02,6.04,9)undecane) and 3,5-dehydronoriceane (pentacyclo(5.3.1.02,6.03,5.04,9)undecane).

もっと見る 閉じる

スポンサーリンク