Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions
Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions
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DOI：
10.1002/1615-4169(200107)343:5
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发表时间：
2001-07
影响因子：
5.4
通讯作者：
Y. Ishii;S. Sakaguchi;T. Iwahama
中科院分区：
文献类型：
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作者：
Y. Ishii;S. Sakaguchi;T. Iwahama
以N-羟基邻苯二甲酰亚胺（NHPI）为关键化合物，实现了温和条件下烃类好氧氧化催化碳自由基生成的创新。采用NHPI与过渡金属Co、Mn的复合催化体系，成功地将烷烃用O2或空气氧化成醇、酮和二元羧酸等有价值的含氧化合物。NHPI催化的分子氧氧化烷基苯反应在常温常压下即可进行。二甲苯和甲基吡啶也分别转化为邻苯二甲酸和吡啶羧酸，产率良好。将现有的氧化方法推广到醇选择性转化为羰基化合物和炔选择性转化为炔酮。在NHPI的作用下，由烃类或醇类与O2反应原位生成氢过氧化物或H2 O2，进行烯烃的环氧化反应，是一种工业应用的有效方法。NHPI方法适用于通过碳自由基中间体的各种有机合成。在NHPI存在下，通过使用CO和O2实现烷烃的催化羧化。此外，NHPI催化烷烃与NO2和SO2的反应分别为硝基烷烃和磺酸的合成提供了有效的方法。在温和条件下，通过烷烃或醇原位生成的碳自由基与烯烃反应，实现了催化碳-碳键形成反应。1引言2 NHPI作为由烷烃产生碳自由基的催化剂的发现2.1历史背景2.2 NHPI在有氧氧化中的催化作用3 NHPI-催化的有氧氧化3.1苄基化合物的氧化3.2烷烃与分子氧的氧化3.3烷基苯的氧化3.4甲基吡啶的实际氧化3.5通过炔氧化制备炔酮3.6氧化3.7硫化物选择性氧化为亚砜3.8通过醇的有氧氧化生产过氧化氢3.9使用分子氧作为末端氧化剂的烯烃环氧化4烷烃与CO和O2的羧化5 NOx在有机合成中的利用5.1使用NO2的烷烃的第一催化硝化5.2 NO与有机化合物的反应6烷烃催化的磺基氧化通过钒7通过NHPI辅助的各种有机化合物产生的催化碳自由基的碳-碳键形成反应7.1烯烃与烷烃和分子氧的烷氧基化7.2通过α-羟基碳自由基与不饱和酯的加成合成α-羟基-γ-内酯7.3使用1，3-二氧戊环和分子氧的烯烃羟基酰化8结论
An innovation of the aerobic oxidation of hydrocarbons through catalytic carbon radical generation under mild conditions was achieved by using N-hydroxyphthalimide (NHPI) as a key compound. Alkanes were successfully oxidized with O2 or air to valuable oxygen-containing compounds such as alcohols, ketones, and dicarboxylic acids by the combined catalytic system of NHPI and a transition metal such as Co or Mn. The NHPI-catalyzed oxidation of alkylbenzenes with dioxygen could be performed even under normal temperature and pressure of dioxygen. Xylenes and methylpyridines were also converted into phthalic acids and pyridinecarboxylic acids, respectively, in good yields. The present oxidation method was extended to the selective transformations of alcohols to carbonyl compounds and of alkynes to ynones. The epoxidation of alkenes using hydroperoxides or H2O2 generated in situ from hydrocarbons or alcohols and O 2 under the influence of the NHPI was demonstrated and seems to be a useful strategy for industrial applications. The NHPI method is applicable to a wide variety of organic syntheses via carbon radical intermediates. The catalytic carboxylation of alkanes was accomplished by the use of CO and O2 in the presence of NHPI. In addition, the reactions of alkanes with NO2 and SO2 catalyzed by NHPI provided efficient methods for the synthesis of nitroalkanes and sulfonic acids, respectively. A catalytic carbon-carbon bond forming reaction was achieved by allowing carbon radicals generated in situ from alkanes or alcohols to react with alkenes under mild conditions. 1 Introduction 2 Discovery of NHPI as Carbon Radical Producing Catalyst from Alkanes 2.1 Historical Background 2.2 Catalysis of NHPI in Aerobic Oxidation 3 NHPI-Catalyzed Aerobic Oxidation 3.1 Oxidation of Benzylic Compounds 3.2 Alkane Oxidations with Molecular Oxygen 3.3 Oxidation of Alkylbenzenes 3.4 Practical Oxidation of Methylpyridines 3.5 Preparation of Acetylenic Ketones via Alkyne Oxidation 3.6 Oxidation of Alcohols 3.7 Selective Oxidation of Sulfides to Sulfoxides 3.8 Production of Hydrogen Peroxide by Aerobic Oxidation of Alcohols 3.9 Epoxidation of Alkenes using Molecular Oxygen as Terminal Oxidant 4 Carboxylation of Alkanes with CO and O2 5 Utilization of NOx in Organic Synthesis 5.1 First Catalytic Nitration of Alkanes using NO2 5.2 Reaction of NO with Organic Compounds 6 Sulfoxidation of Alkanes Catalyzed by Vanadium 7 Carbon-Carbon Bond Forming Reaction via Catalytic Carbon Radicals Generated from Various Organic Compounds Assisted by NHPI 7.1 Oxyalkylation of Alkenes with Alkanes and Dioxygen 7.2 Synthesis of α-Hydroxy-γ-lactones by Addition of α-Hydroxy Carbon Radicals to Unsaturated Esters 7.3 Hydroxyacylation of Alkenes using 1,3-Dioxolanes and Dioxygen 8 Conclusions