Metal Porphyrin-Catalyzed Redutive Oxygenation of Olefins and Its Application

金属卟啉催化烯烃还原氧化反应及其应用

• 批准号: 05650884
• 负责人: MATSUSHITA Yoh-ichi
• 金额: $ 1.28万
• 依托单位: Miyazaki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05650884/
• 关键词: Porphyrin; Cobalt catalyst; Oxygenation; Hydroperoxide; Hydroxylation; Triethylsilane; Conjugated olefin; Nitrosation; 亜硝酸エステル; コバルトポルフィリン; 触媒反応; アルコール; シラン; アクリル酸; 共役ジエンカルボニル化合物

Reduction-oxygenation of alpha, beta, gamma, delta-unsaturated carbonyl compounds with molecular oxygen (1 atm) and triethylsilane in the presence of a catalytic amount of cobalt (II) porphyrin proceeded rapidly and regioselectively to afford gamma-hydroperoxy-alpha, beta-unsaturated carbonyl compounds in good yields. The obtained hydroperoxides were converted in one pot into gamma-hydroxy-alpha, beta-unsaturated carbonyl compounds by reducing with trimethyl phosphite, and into gamma-oxo-alpha, beta-unsaturated carbonyl compounds by treating with acetic anhydride and 4- (N,N-dimethylamino) pyridine.Total synthese of some biologically active natural products were attempted by the application this reductive oxygenation. (-) -Pyrenophorin, a 16-membered antibiotic macrolide, was synthesized via the reductive oxygenation of ethyl (2E,4E,7S) -7-acetoxy-2,4-octadienoate prepared from D-glucose. 6-Hydroxyshojail and related furanoids, new antioxidative compounds isolated from Ginger, were also synthesized in good yields from vanillin.Furthermore, the reductive nitrosation of stirenes and alpha, beta-unsaturated esters with alkyl nitrite and triethylsilane was found to be catalyzed by cobalt (II) porphyrin, to produce acetophenone oximes and alpha-hydroxyimino esters, respectively. Further studies of this nitosation are now in progress in detail.In this reseach, novel and widespread methods for conversion of conjugated olefins into the correponding hydroperoxides, alcohols, and ketones could be established by cobalt (II) porphyrin-catalyzed regioselective oxygenation with molecular oxygen and triethylsilane followed by the appropriate treatment.

在催化量的钴（II）卟啉存在下，α、β、γ、δ不饱和羰基化合物与分子氧（1atm）和三乙基硅烷的还原-氧化迅速进行，区域选择性地产生了产率较高的γ -羟基- α、β -不饱和羰基化合物。得到的氢过氧化物经亚磷酸三甲酯还原得到-羟基- α， -不饱和羰基化合物，经乙酸酐和4- （N，N-二甲氨基）吡啶处理得到-氧- α， -不饱和羰基化合物。应用这种还原性氧化法，尝试了一些具有生物活性的天然产物的全合成。以d -葡萄糖为原料制备(2E,4E,7S) -7-乙酰氧基-2,4-辛二烯酸乙酯，经还原氧化合成(-)- pyrenophorin - 16元抗生素大环内酯。以香兰素为原料，从生姜中分离得到了新的抗氧化化合物6-羟基糠醛及相关呋喃酮。此外，还发现在钴（II）卟啉催化下，苯乙烯和α、β -不饱和酯与烷基亚硝酸盐和三乙基硅烷的还原亚硝化反应可分别生成苯乙酮肟和α -羟亚胺酯。对这种硝化作用的进一步详细研究正在进行中。在本研究中，通过钴（II）卟啉催化与分子氧和三乙基硅烷的区域选择性氧化，然后进行适当的处理，可以建立新的和广泛的将共轭烯烃转化为相应的氢过氧化物、醇和酮的方法。

项目成果

Yoh-chi MATSUSHITA,Hiroshi FURUSAWA,Takanao MATSUI,Mitsuru NAKAYAMA: "Total Synthesis of (-) -Pyrenophorin via Cobalt (II) Porphyrin-Catalyzed Oxygenation of Ethyl (2E,4E,7R) -7-Acetoxy-2,4-octadienoate" Chemistry Letters. 1083-1084 (1994)

Yoh-chi MATSUSHITA、Hiroshi FURUSAWA、Takanao Matsui、Mitsuru NAKAYAMA：“通过钴 (II) 卟啉催化乙基氧化 (2E,4E,7R) -7-乙酰氧基-2,4- 全合成 (-) -核素蛋白

Yoh-ichi MATSUSHITA,Kazuhiro SUGAMOTO,Tuyoshi NAKAMA,Toshifumi SAKAMOTO,Takanao MATSUI,Mitsuru NAKAYAMA: "gamma-Selective Hydroxylation of alpha, beta, gamma, delta-Unsaturated Carbonyl Compounds and Its Application Synthese (<plus-minus>) -6-Hydroxyshoja

Yoh-ichi MATSUSHITA,Kazuhiro SUGAMOTO,Tuyoshi NAKAMA,Toshifumi SAKAMOTO,Takanao MATSUI,Mitsuru NAKAYAMA：“α、β、γ、δ-不饱和羰基化合物的γ选择性羟基化及其应用合成（<正负>）-6

Yoh-ichi MATSUSHITA: "Total Synthesis of (-) -Pyrenophorin via Cobalt (II) Porphyrin-Catalyzed Oxygenation of Ethy1 (2E,4E,7R) -7-Acetoxy-2,4-octadienoate" Chemistry Letters. 1083-1084 (1994)

Yoh-ichi MATSUSHITA：“通过钴 (II) 卟啉催化 Ethy1 (2E,4E,7R) -7-Acetoxy-2,4-octadienoate 氧化全合成 (-)-Pyrenophorin”化学快报。

Yoh-ichi MATSUSHITA: "Synthesis of γ-Hydroperoxy-α, B-unsaturated Carbonyl Compounds from α, B, γ, δ-Unsaturated Carbonyl Compounds by Cobalt (II) Porphyrin-catalyzed Hydroperoxygenation" Journal of the Chemical Society, Chemical Communications. in press.

Yoh-ichi MATSUSHITA：“通过钴 (II) 卟啉催化氢过氧化作用从 α, B, γ, δ-不饱和羰基化合物合成 γ-氢过氧-α, B-不饱和羰基化合物”化学会杂志，化学通讯。在新闻。

Yoh-ichi MATSUSHITA: "γ-Selective Hydroxylation of α,β,γ,δ-Unsaturated Carbonyl Compounds and Its Application to Syntheses of(±)-6-Hydroxyshogaol and Related Furanoids" Tetrahedron Letters. in press (1995)

Yoh-ichi MATSUSHITA：“α,β,γ,δ-不饱和羰基化合物的 γ-选择性羟基化及其在 (±)-6-Hydroxyshogaol 和相关呋喃类化合物合成中的应用”Tetrahedron Letters，出版 (1995)。