Ruthenium-catalyzed carbon-hydrogen bond activation. Oxyfunctionalization of nonactivated carbon-hydrogen bonds in the cedrane series with ruthenium tetraoxide generated in situ
Ruthenium-catalyzed carbon-hydrogen bond activation. Oxyfunctionalization of nonactivated carbon-hydrogen bonds in the cedrane series with ruthenium tetraoxide generated in situ
复制标题
钌催化的碳氢键活化。
DOI：
10.1021/jo00046a040
复制
发表时间：
1992
影响因子：
3.6
通讯作者：
B. Waegell
中科院分区：
文献类型：
--
作者：
A. Tenaglia*;E. Terranova;B. Waegell
饱和烃既不具有未成键的电子对，也不具有低位空轨道。因此，在均相和温和的条件下，这些烃中未活化的CH键的活化和选择性官能化被认为是一个重要且具有挑战性的目标。 1 目前这是一个快速扩展的领域，因为良好的催化剂的定制将允许叔 CH 键的选择性羟基化或亚甲基氧化成酮。该领域最近的研究涉及干臭氧化、1 2 过氧酸、3 超酸介质中的臭氧、4 5 和二环氧乙烷。 6 还使用了过渡金属物质的均相催化。 14 例如，Gif 或相关系统6 特别有趣，因为它们使用双氧。微生物已经证明了它们的效率，尽管产量不是很令人印象深刻。酶经常涉及高价金属氧物种，例如细胞色素 P-4507 以及金属卟啉 8，这构成了主要的研究领域。金属簇9和元素氟10最近作为新的研究领域出现。
Saturated hydrocarbons possess neither unbonded electron pairs nor low-lying empty orbitals. As a conse-quence, the activation and selective functionalizationof nonactivated CH bonds in these hydrocarbons, under homogeneous and mild conditions, is recognized as an important and challenging objective. 1 This is presently a rapidly expanding field because the tailoringof good catalysts would allow for selective hydroxylation of tertiary CH bonds or oxidation of methylenegroups into ketones. Recent studies in this area involve dry ozonation, 1 2 peroxy acids, 3 ozone in superacid media, 4 5and dioxirane. 6 Ho-mogeneous catalysis with transition-metal species has also been used. 14 For instance, the Gif or related systems6 are especially interesting because they use dioxygen. Mi-croorganisms have proven their efficiency even through the yields are not very impressive. Enzymes frequently involve a high-valent metal-oxo species such as cytochrome P-4507 along with metalloporphyrins8 which constitutes a major area of research. Metallic clusters9 and elemental fluorine10 have appeared recently as new fields of inves-tigation.