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

描述（由申请人提供）：伯醇是日用品和医药化学工业中的重要分子。目前，它们的大规模生产涉及使用有毒和危险的一氧化碳和氢气的高压，或化学计量的金属和过氧化物试剂。一种通过从容易获得的烯烃前体进行反马尔可夫尼科夫水合来直接催化合成它们的新方法将有益于生物活性小分子以及有益于人类健康和生活质量的聚合物和商品化学品的合成。目前对该问题的解决方案要么需要多步程序、化学计量量的氧化剂和/或还原剂，要么在范围上受到限制。提出了一种反马氏水合的一般方法，通过自由基加成到烯烃，这提供了更高度取代的自由基中间体。开发了一种新的催化循环，其中氢原子从金属-羟基物种转移产生新的碳-氢键，并通过再生金属-氧代催化剂来传播自由基反应。该循环涉及两种相互交换氧化态的有机金属物质，使得反应在不需要外源氧化剂或还原剂的情况下进行。这种双模式催化将促进双核有机金属框架的设计，其中金属-氧代和金属-羟组分是存在于紧密接近。这种方法允许氢原子转移由于其是分子内过程的性质而被加速，并且在双核氧化还原转移中产生形式对称性。锰氧代配合物已被确定为理想的起点，由于其已知的自由基型反应性在氧原子转移和氢原子转移反应。由于自由基反应的典型高官能团耐受性，预期从该提议开发的烯烃水合催化剂具有一般范围，允许从容易获得的烯烃原料合成宽范围的醇。

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.