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    • 2. 发明公开
    • PREPARATION AND APPLICATIONS OF POLYMER-SUPPORTED HALOGENATED BENZOQUINONES AS OXIDATIVE AGENTS
    • HERSTELLUNG UND ANWENDUNGEN VONPOLYMERGETRÄGERTENHALOGENITENTEN BENZOCHINONEN ALS OxyidationSMITTEL
    • EP1758850A1
    • 2007-03-07
    • EP04736534.1
    • 2004-06-10
    • COULADOUROS, Elias, AndreaStrongilos, Alexandros
    • COULADOUROS, Elias, AndreaStrongilos, Alexandros
    • C07C255/46C07C317/44C07B33/00C07J75/00
    • C07C255/57C07B2200/11C07C255/53C07C255/54C07C255/55C07C317/44C07C2601/16C07J75/00Y02P20/55
    • This invention provides a general method for the synthesis of polymer-supported benzoquinones described by the following generic structure I: wherein: •, X, R1, R2 and R3 are described in the main text. The general concept of the method consists of the use of a halogenated starting material of the general structure II (Figure 1) which by an nucleophilic substitution reaction (NSR) or a palladium mediated coupling (PMC) is either directly loaded on a resin to afford IIIa (Path A) or transformed to intermediate IIIb (Path B) which is subsequently (with or without modification) loaded on a resin to afford once again IIIa. Deprotection and/or oxidation of IIIa, if needed, afford target solid-supported oxidants I The polymer-supported benzoquinones I are used for the oxidation of hydroquinones to quinones, for the oxidation of benzylic alcohols the aldehydes, for the removal of p-methoxybenzyl and related protective groups, for the dehydrogenation of tetrahydronaphthalene derivatives and for the dehydrogenation of steroid 4-en-3-ones. The polymer-supported reagent after its use is regenerated upon treatment with an oxidative agent.
    • 本发明提供了通过以下通用结构I描述的合成聚合物负载的苯醌的一般方法:其中:。,X,R 1,R 2和R 3在正文中描述。 该方法的一般概念包括使用一般结构II(图1)的卤化起始材料,其通过亲核取代反应(NSR)或钯介导的偶联(PMC)直接负载在树脂上以提供 IIIa(路径A)或转化成中间体IIIb(路径B),其随后(有或没有改性)负载在树脂上以再次提供IIIa。 如果需要,IIIa的脱保护和/或氧化提供目标固体负载的氧化剂I聚合物负载的苯醌I用于将氢醌氧化成醌,用于苄基醇的氧化醛,用于除去对甲氧基苄基 和相关的保护基团,用于四氢萘衍生物的脱氢和类固醇4-烯-3-酮的脱氢。 使用后的聚合物负载的试剂在用氧化剂处理时再生。