29 6員環上アリル位2級アルコールの立体配座とアセテート則

スポンサーリンク

概要

• 論文の詳細を見る

• A rule concerning the determination of the conformation and configuration of the allylic (benzylic) hydroxyl group in 1-tetralols or 4-chromanols by NMR measurement was elaborated. The rule consists of the comparison of the acetylation mobility (Δ Ac), the differrence in chemical shifts of allylic protons between the alcohols and the corresponding acetates, for a pair of isomers, while the conventional method comprises the determination of the vicinal coupling between the allylic proton in question and the proton on the adjacent carbon atom. It was found that the value (Δ Ac_<eq>) for quasi-equatorial proton of one isomer was always larger than that (Δ Ac_<ax>) for quasi-axial proton of the counterpart. This regularity should be attributed to the preferred orientation of the O-H bond for axial and equatorial conformation and to the resulting anisotropic deshielding effect of electron lone pairs of the hydroxyl oxygen. This "Acetate Rule" could successfully be applied to the stereochemical assignment of several 1-tetralol and 4-chromanol derivatives and natural products. For example, the value (Δ Ac in CDCl_3) larger than 1,24 corresponds to the quasi-axial allylic hydroxyl, and that smaller than 1,17 to the quasi-equatorial one in simple flavanols.

• 天然有機化合物討論会の論文
• 1974-10-01

著者

• 尾崎 裕

  Faculty Of Pharmaceutical Sciences Osaka University

• 百瀬 雄章

  Faculty Of Pharmaceutical Sciences Osaka University

• 百瀬 雄章

  阪大薬

• 尾崎 裕

  阪大薬

• 百瀬 雄章

  Faculty Of Pharmaceutical Sciences Kanazawa University

関連論文

• A New Method for the Preparation of Michael Adducts and Cyclic Enones Using Lithium Chloride-Hexamethylphosphoramide System
• A New Synthesis of the Aporphine Alkaloids (±)-Glaucine and(±)-Nantenine. Application of [3C + 3C] Annelation to the D-Ring Formation
• A NEW SYNTHESIS OF THE APORPHINE ALKALOIDS (±)-GLAUCINE AND (±)-NANTENINE
• A New Entry to the Synthesis of 1,2-Benzenediol Congeners
• A NEW ENTRY TO 1,2-BENZENEDIOL CONGENERS
• A New Synthesis of 1,2,4-Benzentriol Congeners
• Aromatic Annelation with α-PhenyIsulfinyl-γ-butyrolactones. A Novel Route to 4-(2-Hydroxyalkyl)-1,3-benzenediols(Organic,Chemical)
• Stereospecific Synthesis of cis- and trans-2,3-Epoxycycloheptanol
• 新しい入試制度を体験して
• Favorskii Reaction of 2-Bromobicyclo[3.3.1]nonan-3-one
• 1,6-Dihydro-3 (2H)-pyridinones. II. Synthesis of 2-Azabicyclo [2. 2. 2] octanes by the Reaction of N-Substituted 1,6-Dihydro-3 (2H)-pyridinones with 1,3-Dicarbonyl Compounds
• 1,6-Dihydro-3 (2H)-pyridinones. I. Facile Synthesis of N-Substituted 1,6-Dihydro-3 (2H)-pyridinones
• 含窒素共役系の反応(第8報)Dimethyl Inidazole-4,5-dicarboxylateとAnetholeとの反応生成物の構造について
• 含窒素共役系の反応(第7報)N-CinnamylidenemethylamineとN-Methyl-maleimideとめ付加体について
• 含窒素共役系の反応(第6報)2,3-Diphenyl-5,6-dihydropyrazineとDiethyl FumarateまたはN-Methylmaleimideとの付加体の立体構造について
• Synthetic Studies on Anthracyclinones. XIII. Conversion of Bisanhydro-γ-rhodomycinone into Bisanhydrodaunomycinone
• Synthetic Studies on Anthracylinones. XI. Abnormal Products from Phenolic Compounds on Methylation with Dimethyl Sulfate in Tetrahydrofuran
• Anthracyclinone類の合成研究(第10報) : Methyl 2-(1-Acetoxy-3-oxobutyl)phenylacetateの合成
• Synthesis of Bisanhydrodaunomycinone
• The Preparation of Fused Ring α, β-Unsaturated Lactones using Lithium Ethoxyacetylide. Syntheses of Dihydroactinidiolide and Actinidiolide, and Partial Synthesis of Dihydrosecurinine
• Synthetic Studies on Lignans and Related Compounds. VIII. : Synthesis of Justicidin B and Diphyllin and of Taiwanin C and E from 2,3-Dibenzylidenebutyrolactones via β-Apolignans : A Chemical Model for Natural Co-occurrence of 4-Hydrogen-and 4-Hydroxy-1-ph
• Synthetic Studies on Lignans and Related Compounds. VII. : Synthesis of β-Apoplicatitoxin Trimethyl Ether
• Synthetic Studies on Lignans and Related Compounds. VI. Photochemical Rearrangement of β-Apolignans
• Synthetic Studies on Lignans and Related Compounds. V. Regiospecificity in the Photocyclization of 2,3-Dibenzylidenebutyrolactones
• Synthetic Studies on Lignans and Related Compounds. IV. Synthesis of Taiwanin C and E, and Justicidin D (Neojusticin A), E, and F (Taiwanin E Methyl Ether)
• 2(3H)- and 2(5H)-Furanones. IV. The Di-π-methane Rearrangement of 3,4-Bis(phenymethyl)-2(5H)-furanone
• 85 2-Alkyl-ω-azabicyclo[3.n.1]alkan-3-one類の位置選択的α開裂を利用したα,α'位シス置換ピペリジン及びピロリジンアルカロイドの合成(ポスター発表の部)
• Marine Natural Products. XXVI. Biologically Active Tridecapeptide Lactones from the Okinawan Marine Sponge Theonella swinhoei(Theonellidae).(2).Structures of Theonellapeptolides Ia, Ib, Ic, and Ie
• Bicyclo[3.3.1]nonanes as Synthetic Intermediates. XVII. : A Novel Interconversion between Bicyclo-[4.3.1]decane and Tricyclo[4.3.1.0]decane Systems via the Dual Mode of Aldol Cyclization of Bicyclo-[4.3.1]decane-3,8-dione
• Bicyclo[3.3.1]nonanes as Synthetic Intermediates. XVI. On the Selectivity in the Ring Enlargement of the Bicyclo[3.3.1]nonan-2-one System
• Bicyclo[3.3.1]nonanes as Synthetic Intermediates. XV. : Ring Enlargement of Bicyclo[3.3.1]nonane-2,6-dione and Bicyclo[3.3.1]nonan-2-one; Revision of the Literature
• Bicyclo [3. 3. 1] nonanes as Synthetic Intermediates. IX. Photo-Irradiation of Bicyclo [3....1] alkan-3-one in Cyclohexane : A Selective Photo-Reduction with Predominance of endo-Hydrogenation
• 3-Hydroxypyrroles. III. Synthesis and Tautomerism of N-Alkyl-3-hydroxypyrroles
• Bicyclo [3. 3. 1] nonanes as Synthetic Intermediates. V. The Baeyer-Villiger Oxidation of Bicyclo [3. 3. 1] nonane-3,7-dione and Its Congeners
• Bicyclo [3. 3. 1]nonanes as Synthetic Intermediates. IV. Behavior of Bicyclo [3. n. 1] alkan-3-ones toward the Baeyer-Villiger Oxidation
• Octahydro-7 (1H)-quinolones. VII. A Stereoselective Synthesis of cis, trans-Decahydro-3H, 8H-benzo [i, j] quinolizine-3,8-dione
• 3-Hydroxypyrroles. II. The Reaction of 4,5-Unsubstituted Alkyl 3-Hydroxypyrrole-2-carboxylates with Some Electrophiles
• Bicyclo [3. 3. 1] nonanes as Synthetic Intermediates. III. The Baeyer-Villiger Oxidation of Some Bicycloalkyl Phenyl Ketones
• 10 リコポジウムアルカロイドの合成研究 : (±)-Anhydrolycodoline及び(±)-Lycopodineの全合成
• TOTAL SYNTHESIS OF (+)-MONOMORINE I VIA ASYMMETRIC α-KETONIC CLEAVAGE OF 8-AZABICYCLO[3.2.1]OCTAN-3-ONE
• Synthetic Studies on Anthracyclinones. XIV. On the Conformational Aspects of Ring A of Daunomycinone : A Model Study
• 29 6員環上アリル位2級アルコールの立体配座とアセテート則
• 26 Anthracyclinoneの合成
• Synthetic Studies on η-Pyrromycinone. V. Total Synthesis of η-Pyrromycinone
• Synthetic Studies on η-Pyrromycinone. IV. Conversion of 1,11-Dimethoxy-5(12H)-naphthacenones into 4,6-Dimethoxynaphthacenequinones by Chromium Trioxide Oxidation
• Synthetic Studies on η-Pyrromycinone. III. Intramolecular Cyclization of methyl 2-Ethyl-5-hydroxy-6-(2-carboxy-3,6-dimethoxybenzoyl)-1-naphthoate
• Synthetic Studies on η-Pyrromycinone II. Synthesis of Methyl 2-Ethyl-5-Hydroxy-1-naphthoate
• Synthetic Studies on Anthracyclinones. IX. Lithiation of N, N-Dimethylnaphthalenemethylamines and a New Synthetic Pathway to 2,3-Naphthalides
• Synthetic Studies on Lignans and Related Compounds. III. Structure and Synthesis of Diphyllin
• Synthetic Studies on Lignans and Related Compounds. II. Synthesis of 1-Hydroxy-3-hydroxymethyl-6,7-dimethoxy-4-(3,4-methylenedioxyphenyl)-2-naphthoic Acid γ-Lactone and Its Non-identity with Diphyllin
• Synthetic Studies on Lignans and Related Compounds. I. Synthesis of 1-Hydroxy-3-hydroxymethyl-4-(3,4-dimethoxyphenyl)-6,7-methylenedioxy-2-naphthoic Acid γ-Lactone
• 22 Diphyllinの構造と合成
• 3-Hydroxypyrroles. I. A General Synthetic Route to 4,5-Unsubstituted Alkyl 3-Hydroxypyrrole-2-carboxylates
• Synthetic Studies on Anthracyclinones. XII. Synthesis of 8-Ethyl-1,6,11-trihydroxynaphthacenequinone
• Bicyclo [3. 3. 1] nonanes as Synthetic Intermediates. II. Synthesis of Bicyclo [3. n. 1] alkan-3-one via α, α'Annelation of Cycloalkanone
• Bicyclo [3.3.1] nonanes as Synthetic Intermediates. I. Improved Synthetic Methods for Bicyclo [3.3.1] nonan-3-one
• Octahydro-7 (1H)-quinolones. IV. Construction of Decahydro-3H, 10H-benzo [i, j] quinolizine-3,10-dione Systems from cis-and trans-Octahydro-7 (1H)-quinolone
• Octahydro-7 (1H)-quinolones. III. cis-trans Isomerization of Octahydro-7 (1H)-quinolone Analogues
• Octahydro-7 (1H)-quinolones. II. A Stereoselective Synthesis of cis-Octahydro-7 (1H)-quinolone
• Octahydro-7 (1H)-quinolones. I. Stereochemistries of Catalytic Hydrogenation of 7-Hydroxyquinoline
• Synthesis of (±)-Hydroxysugiresinol (Sequirin B) Trimethyl Ether
• Synthetic Studies on the Lycopodium Alkaloids. III. Synthesis of a Key Intermediate, Ethyl Octahydro-4aβ-hydroxy-7β-methyl-10-oxo-1H-5,8α-propanoquinoline-1-carbamate, for the Lycopodium Alkaloids
• The Structures of Securinol B and C
• Synthetic Studies on Anthracyclinones. VIII. Synthesis of 4-Bromo-6-ethyl-1-naphthol
• Synthetic Studies on Anthracyclinones. VII. Synthesis of Bisanhydroaklavinone
• Synthetic Studies on Anthracyclinones. VI. The Friedel-Crafts Condensation between 3-Methoxyphthalic Anhydride and α-Naphthol Derivatives
• Synthesis of Bisanhydroaklavinone
• 2-Acetyl-1-naphthoic and 2-Acetyl-3,4-dihydro-1-naphthoic Acid.
• Conversion of Methyl 2-Ethyl-6,11-dihydro-6,11-dioxo-5,7,10-trimethoxy-1-naphthacenecarboxylate into η-Pyrromycinone
• Synthesis of Methyl 2-Ethyl-6,11-dioxo-5,7,10-trimethoxy-6,11-dihydro-1-naphthacenecarboxylate (η-Pyrromycinone Trimethyl Ether)

もっと見る 閉じる

スポンサーリンク