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

基本信息

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

项目摘要

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 (1 atm) 和三乙基硅烷的还原氧化反应快速且区域选择性地进行，得到γ-氢过氧-α、β -不饱和羰基化合物的产率良好。所得氢过氧化物用亚磷酸三甲酯还原，一锅转化为γ-羟基-α，β-不饱和羰基化合物，用乙酸酐和4-(N， N-二甲氨基)吡啶。应用这种还原氧化作用尝试全合成一些具有生物活性的天然产物。 (-)-Pyrenophorin 是一种 16 元抗生素大环内酯，通过由 D-葡萄糖制备的 (2E,4E,7S)-7-乙酰氧基-2,4-辛二烯酸乙酯的还原氧化合成。 6-Hydroxyshojail 和相关呋喃类化合物是从生姜中分离出来的新型抗氧化化合物，也可以从香草醛中以良好的产率合成。此外，还发现苯乙烯和 α,β-不饱和酯与亚硝酸烷基酯和三乙基硅烷的还原亚硝化反应是由钴催化的（ II) 卟啉，分别产生苯乙酮肟和α-肟基酯。目前对该亚硝基化的进一步研究正在进行中。在这项研究中，通过钴（II）卟啉催化的分子氧区域选择性氧化，可以建立将共轭烯烃转化为相应的氢过氧化物、醇和酮的新颖且广泛的方法。和三乙基硅烷，然后进行适当的处理。