Młochowski Jacek, Wójtowicz-Młochowska Halina
Faculty of Chemistry, Wroclaw University of Technology, Wybrzeże Wyspiańskiego 27, Wroclaw 50-370, Poland.
Molecules. 2015 Jun 3;20(6):10205-43. doi: 10.3390/molecules200610205.
A variety of selenium compounds were proven to be useful reagents and catalysts for organic synthesis over the past several decades. The most interesting aspect, which emerged in recent years, concerns application of hydroperoxide/selenium(IV) oxide and hydroperoxide/organoselenium catalyst systems, as "green reagents" for the oxidation of different organic functional groups. The topic of oxidations catalyzed by organoselenium derivatives has rapidly expanded in the last fifteen years This paper is devoted to the synthetic applications of the oxidation reactions mediated by selenium compounds such as selenium(IV) oxide, areneseleninic acids, their anhydrides, selenides, diselenides, benzisoselenazol-3(2H)-ones and other less often used other organoselenium compounds. All these compounds have been successfully applied for various oxidations useful in practical organic syntheses such as epoxidation, 1,2-dihydroxylation, and α-oxyfunctionalization of alkenes, as well as for ring contraction of cycloalkanones, conversion of halomethyl, hydroxymethyl or active methylene groups into formyl groups, oxidation of carbonyl compounds into carboxylic acids and/or lactones, sulfides into sulfoxides, and secondary amines into nitrones and regeneration of parent carbonyl compounds from their azomethine derivatives. Other reactions such as dehydrogenation and aromatization, active carbon-carbon bond cleavage, oxidative amidation, bromolactonization and oxidation of bromide for subsequent reactions with alkenes are also successfully mediated by selenium (IV) oxide or organoselenium compounds. The oxidation mechanisms of ionic or free radical character depending on the substrate and oxidant are discussed. Coverage of the literature up to early 2015 is provided. Links have been made to reviews that summarize earlier literature and to the methods of preparation of organoselenium reagents and catalysts.
在过去几十年中，多种硒化合物被证明是有机合成中有用的试剂和催化剂。近年来出现的最有趣的方面是氢过氧化物/二氧化硒和氢过氧化物/有机硒催化剂体系作为氧化不同有机官能团的“绿色试剂”的应用。在过去十五年中，有机硒衍生物催化氧化的主题迅速扩展。本文致力于硒化合物介导的氧化反应的合成应用，这些硒化合物包括二氧化硒、芳基硒酸、它们的酸酐、硒化物、二硒化物、苯并异硒唑-3(2H)-酮以及其他较少使用的有机硒化合物。所有这些化合物已成功应用于各种实际有机合成中有用的氧化反应，如烯烃的环氧化、1,2-二羟基化和α-氧官能化，以及环烷酮的环收缩、卤甲基、羟甲基或活性亚甲基转化为甲酰基、羰基化合物氧化为羧酸和/或内酯、硫化物氧化为亚砜、仲胺氧化为硝酮以及从它们的偶氮甲碱衍生物再生母体羰基化合物。其他反应，如脱氢和芳构化、活性碳-碳键断裂、氧化酰胺化、溴内酯化以及溴化物氧化以用于随后与烯烃的反应，也成功地由二氧化硒或有机硒化合物介导。讨论了取决于底物和氧化剂的离子或自由基性质的氧化机理。提供了截至2015年初的文献综述。还链接了总结早期文献的综述以及有机硒试剂和催化剂的制备方法。
