Design, Synthesis and Evaluation of Radical-Based Catalysts for the Direct Anti-M

描述（申请人提供）：伯醇是商品和医药化工行业的重要分子。目前，它们的大规模生产涉及使用高压有毒和危险的一氧化碳和氢气气体，或化学计量金属和过氧化物试剂。利用现成的烯烃前体通过反马尔可夫尼科夫水合作用直接催化合成它们的新方法，将有利于合成生物活性小分子，以及有利于人类健康和生活质量的聚合物和商品化学品。目前解决这一问题的方法要么需要多步骤程序，要么需要化学计量量的氧化剂和/或还原剂，要么范围有限。提出了一种反马尔可夫尼科夫水化的一般方法，即通过自由基加成烯烃，它提供了更高取代的自由基中间体。建立了一种新的催化循环，其中氢原子从金属-羟基转移产生新的碳氢键，并通过再生金属-氧催化剂来传播自由基反应。这个循环涉及两种氧化态互换的有机金属，使反应无需外源氧化剂或还原剂即可进行。这种双模式催化将通过设计双核有机金属框架来促进，其中金属-氧和金属-羟基成分紧密地存在。这种方法允许氢原子转移由于其是分子内过程的性质而加速，并在双核氧化还原转移中产生形式对称。锰氧配合物在氧原子转移和氢原子转移反应中都具有自由基型反应活性，因此被认为是这项研究的理想起点。根据该建议开发的烯烃水合催化剂由于对自由基反应具有典型的高官能团耐受性，预计将具有广泛的应用范围，允许从现成的烯烃原料合成各种醇。

DESCRIPTION (provided by applicant): Primary alcohols are important molecules in both the commodity and pharmaceutical chemical industries. Currently, their large-scale production involves the use of either high pressures of toxic and hazardous carbon monoxide and hydrogen gasses, or stoichiometric metal and peroxide reagents. A new method for their direct, catalytic synthesis by anti-Markovnikov hydration from readily available olefin precursors would be beneficial for the synthesis of bioactive small molecules, as well as polymers and commodity chemicals that benefit human health and quality of life. Current solutions to this problem either require multistep procedures, stoichiometric amounts of oxidant and/or reductant, or are limited in scope. A general approach to anti- Markovnikov hydration is proposed to proceed through radical addition to olefins, which provide the more highly substituted radical intermediate. A new catalytic cycle is developed where hydrogen atom transfer from a metal-hydroxo species generates the new carbon-hydrogen bond and propagates the radical reaction be regenerating the metal-oxo catalyst. This cycle involves two organometallic species of interchanging oxidation states, allowing reaction to proceed without the need for exogenous oxidants or reductants. This dual-mode catalysis will be facilitated by the design of dinuclear organometallic frameworks where the metal-oxo and the metal-hydroxo components are present in close proximity. This approach allows for hydrogen atom transfer to be accelerated by nature of it being an intramolecular process, and creates formal symmetry in the dinuclear redox transfer. Manganese oxo complexes have been identified as the ideal starting point for this investigation due to their known radical-type reactivity in both oxygen atom transfer and hydrogen atom transfer reactions. Olefin hydration catalysts developed from this proposal are anticipated to have general scope due to the typically high functional-group tolerance of radical reactions, allowing a wide range of alcohols to be synthesized from readily available olefin feedstocks.