Oxidation with Hypervalent Peroxyiodinanes

（tert-Butylperoxy） iodanes were found to be a useful oxidizing reagent in organic synthesis.1） They oxidizes benzyl and allyl ethers to the esters at room temperature in the presence of alkali metal carbonates via a radical process。因为这种反应与其他保护组相兼容，所以MOM、THP和TBDMS ethers和乙酰氧组，因为这种反应在基本条件下已经氢化，所以这种方法提供了一种方便和有效的替代方法，以消除苯和乙酰醚的常规减少保护。2）氧化硫基与（叔丁基过氧化物）乙腈-水中或二氯甲烷中的硫代，在高温下生长硫代。对三甲苯在乙腈-水中的氧化物的物质效应进行了测试，对BF 3·Et 20的作用很好，作为一种自由基清道夫、加维诺氧基对二胺的反应。（叔丁基过氧化物）碘代因在K2 CO 3的存在中产生的负离子体，在没有碱性产品的三胺氧化时，会产生三丁基过氧化物胺乙酸酯。（tert-butylperoxy） iodane undergoes氧化物对甲基苯二氮原子的氧化（α）（或碳酸酯） yielding imides或ter-butylperoxyamide acetals，取决于反应条件。一种提议的机制不可能产生碳基分子α到硝基原子。5）由（叔丁基过氧化物）碘在四丁基羟基化合物中选择性地4-（叔丁基过氧化物）-2，5-环己烯-1-酮在良好的年份中氧化4-（叔丁基过氧化物）-2，5-环己烯-1-酮。对自由基分子的参与的证据是被发现的。

(tert-Butylperoxy) iodanes were found to be a useful oxidizing reagent in organic synthesis.1) They oxidizes benzyl and allyl ethers to the esters at room temperature in the presence of alkali metal carbonates via a radical process. Because this reaction is compatible with other protecting groups such as MOM, THP, and TBDMS ethers, and acetoxy groups, and because esters are readily hydrolyzed under basic conditions, this method provides a convenient and effective alternative to the usual reductive deprotection of benzyl and allyl ethers.2) Oxidation of sulfides with the (tert-butylperoxy) iodane in acetonitrile-water or in dichloromethane, yielding sulfoxides in high yields. Substituent effects were examined for the oxidation of thioanisoles in acetonitrile-water in the presence and the absence of BF3・Et20 as well as effects of a free-radical scavenger, galvinoxyl.3) Reaction of secondary amines with (tert-butylperoxy) iodane undergoes dehydrogenation to afford imines in the presence of K2CO3, while oxidation of tertiary amines without base produces tert-butylperoxyamino acetals.4) (tert-butylperoxy) iodane undergoes oxidation of the methlene groups α to the nitrogen atom of amides (or carbamates) yielding imides or tert-butylperoxyamide acetals, depending on the reaction conditions. A proposed mechanism involves generation of carbon-centered radicals α to the nitrogen atom.5) Oxidation of 4-alkylphenols by (tert-butylperoxy) iodane in the presence of tert-butylhydroperoxide affords selectively 4-(tert-butylperoxy)-2,5-cyclohexadien-1-ones in good yields. Evidence for the involvement of free-radicals was obtained.