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Exploitation of Nitroxyl Radidal-type Organocatalysts for Alcohol Oxidation and their Use in Fine Synthetic Chemistry

硝基自由基型醇氧化有机催化剂的开发及其在精细合成化学中的应用

基本信息

批准号：
17390002
负责人：
IWABUCHI Yoshiharu
金额：
$ 9.89万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2007
项目状态：
已结题

项目摘要

This research project aimed exploitation of synthetic potential of azaadamantane N-oxyl (AZADO)-type nitroxyl radicals as oxidation catalyst for alcohol oxidation and their use in fine synthetic chemistry. We have established the following matters in this research period.(1) The structure-activity correlation of AZADO-type nitroxyl radicals: We synthesized a panel of AZADO-type catalysts and examined their function as oxidation catalyst to clarify the molecular basis of the extremely aggressive nature of AZADO compare to TEMPO. Our experiments have led the conclusion that alleviation of the steric factor near the catalytically active site critically determine the catalytic activity.(2) We have developed several synthetic route to enantiomerically modified AZADOs and have examined their use as enantioselective catalyst for oxidation of secondary alcohols. The results allowed us to develop a tentative mechanistic hypothetic model, which is useful for further development.(3) We have developed a ractical and highly efficient methods for oxidative rearrangement of tertiary allylic alcohols to β-substituted α,β-unsaturated ketones employing oxoxammonium salts. The methods developed are applicable to acyclic substrates as well as medium membered ring substrates and macrocyclic substrates. We have elucidated that counter anion of the oxoxmmonium salt plays crucial roles on this oxidative rearrangement.(4) We have discovered a novel AZADO derivative that made us possible to conduct metal-free, halogen-free aerobic oxidation of aloohols to carbonyl compounds under an ambient temperature.

本研究旨在开发氮杂金刚烷-N-氧基(AZADO)类氮氧自由基作为醇氧化催化剂的合成潜力及其在精细合成化学中的应用。(1)氮杂多型氮氧自由基的构效关系：我们合成了一组氮杂多型催化剂，并考察了它们作为氧化催化剂的功能，以阐明氮杂多型相对于TEMPO具有极强侵略性的分子基础。我们的实验得出结论，催化活性中心附近的空间因子的减少是决定催化活性的关键。(2)我们开发了几条合成路线，并考察了它们作为仲醇氧化对映体选择性催化剂的应用。这些结果使我们能够开发出一个初步的机理假设模型，这对进一步的开发是有用的。(3)我们开发了一种实用而高效的方法来催化叔烯丙醇氧化重排生成β取代的α，β-不饱和酮。所开发的方法不仅适用于非环底物，也适用于中元环底物和大环底物。我们发现了一种新型的AZADO衍生物，使我们能够在常温下将芦荟进行无金属、无卤素的有氧氧化生成羰基化合物。