Metal Porphyrin-Catalyzed Redutive Oxygenation of Olefins and Its Application

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。

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.