Bio‐inspired Nonheme Iron Oxidation Catalysis: Involvement of Oxoiron(V) Oxidants in Cleaving Strong C?H Bonds

Kal Subhasree; Xu Shuangning; Que Lawrence

摘要

Abstract >Nonheme iron enzymes generate powerful and versatile oxidants that perform a wide range of oxidation reactions, including the functionalization of inert C?H bonds, which is a major challenge for chemists. The oxidative abilities of these enzymes have inspired bioinorganic chemists to design synthetic models to mimic their ability to perform some of the most difficult oxidation reactions and study the mechanisms of such transformations. Iron‐oxygen intermediates like iron(III)‐hydroperoxo and high‐valent iron‐oxo species have been trapped and identified in investigations of these bio‐inspired catalytic systems, with the latter proposed to be the active oxidant for most of these systems. In this Review, we highlight the recent spectroscopic and mechanistic advances that have shed light on the various pathways that can be accessed by bio‐inspired nonheme iron systems to form the high‐valent iron‐oxo intermediates. </abstract> </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> <div class="translation abstracttxt"> <span class="zhankaihshouqi fivelineshidden" id="abstract"> <span>机译：</span><Abstract Type =“Main”XML：Lang =“en”> <标题类型=“main”>抽象</ title> >非血液铁酶产生强大而通用的氧化剂，具有宽范围的氧化反应，包括惰性C的官能化的官能化。H键，这是化学家的主要挑战。这些酶的氧化能力已经启发了生物碱性化学家来设计合成模型以模仿其进行一些最难以氧化反应的能力，并研究这种转化的机制。铁（III）氧化铁（III） - 羟基（III）的中间体被捕获并鉴定在这些生物启发催化系统的研究中，后者提出是大多数这些系统的活性氧化剂。在本综述中，我们突出了最近的光谱和机械前进，即在各种途径上具有脱光，可以通过生物启发的无血铁系统可以进入，以形成高价铁氧烷中间体。</ p> </摘要> </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> </div> <div class="record"> <h2 class="all_title" id="enpatent33" >著录项</h2> <ul> <li> <span class="lefttit">来源</span> <div style="width: 86%;vertical-align: text-top;display: inline-block;"> <a href='/journal-foreign-19011/'>《Angewandte Chemie》</a> <b style="margin: 0 2px;">|</b><span>2020年第19期</span><b style="margin: 0 2px;">|</b><span>共18页</span> </div> </li> <li> <div class="author"> <span class="lefttit">作者</span> <p id="fAuthorthree" class="threelineshidden zhankaihshouqi"> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Kal Subhasree&option=202" target="_blank" rel="nofollow">Kal Subhasree;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Xu Shuangning&option=202" target="_blank" rel="nofollow">Xu Shuangning;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Que Lawrence&option=202" target="_blank" rel="nofollow">Que Lawrence;</a> </p> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zkzz" style="display: none;">展开▼</span> </div> </li> <li> <div style="display: flex;"> <span class="lefttit">作者单位</span> <div style="position: relative;margin-left: 3px;max-width: 639px;"> <div class="threelineshidden zhankaihshouqi" id="fOrgthree"> <p>Department of ChemistryUniversity of Minnesota Twin Cities207 Pleasant Street SE Minneapolis MN 55455 USA;</p> <p>Department of ChemistryUniversity of Minnesota Twin Cities207 Pleasant Street SE Minneapolis MN 55455 USA;</p> <p>Department of ChemistryUniversity of Minnesota Twin Cities207 Pleasant Street SE Minneapolis MN 55455 USA;</p> </div> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zhdw" style="display: none;">展开▼</span> </div> </div> </li> <li > <span class="lefttit">收录信息</span> <span style="width: 86%;vertical-align: text-top;display: inline-block;"></span> </li> <li> <span class="lefttit">原文格式</span> <span>PDF</span> </li> <li> <span class="lefttit">正文语种</span> <span>eng</span> </li> <li> <span class="lefttit">中图分类</span> <span><a href="https://www.zhangqiaokeyan.com/clc/1188.html" title="应用化学">应用化学;</a></span> </li> <li class="antistop"> <span class="lefttit">关键词</span> <p style="width: 86%;vertical-align: text-top;"> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=C?H bond cleavage&option=203" rel="nofollow">C?H bond cleavage;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=high-valent iron-oxo species&option=203" rel="nofollow">high-valent iron-oxo species;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=nonheme iron enzymes&option=203" rel="nofollow">nonheme iron enzymes;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=oxidation catalysis&option=203" rel="nofollow">oxidation catalysis;</a> </p> <div class="translation"> 机译：C？H键切割;高价铁氧烷种类;非血液铁酶;氧化催化; 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initial;overflow: initial;"> <span>机译：从火力发电厂的气流中除去氮氧化物和硫氧化物的方法，包括用液相中的强氧化剂洗涤气流，并吹扫含有硫酸和硝酸的水溶液 </span> </p> </li> <li> <div> <b>4. </b><a class="enjiyixqcontent" href="/patent-detail/06130443684172.html">Recovery of noble metal, especially gold, from production residue, e.g. sludge, dross or polishing dust, involves dissolution in aqueous thiocyanate solution by adding strong oxidant, e.g. sodium peroxydisulfate or peroxide</a> <b>[P]</b> . <span> 外国专利：  DE10211084C1 </span> <span> . 2003-08-07</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：从生产残渣中回收贵金属特别是金污泥，浮渣或抛光粉尘涉及通过加入强氧化剂（例如过氧二硫酸钠或过氧化物 </span> </p> </li> <li> <div> <b>5. </b><a class="enjiyixqcontent" href="/patent-detail/06130445881464.html">Preparation of fatty acid esters of primary or secondary alcohols, used in production of bio-diesel, from unpurified oil containing fatty acids and sludge involves acid catalysis, base catalysis and glycerin separation</a> <b>[P]</b> . <span> 外国专利：  DE10063967A1 </span> <span> . 2002-06-06</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：由未纯化的含脂肪酸和污泥的油制备用于生产生物柴油的伯醇或仲醇脂肪酸酯涉及酸催化，碱催化和甘油分离 </span> </p> </li> </ul> </div> </div> </div> <div class="theme cardcommon" style="overflow: auto;display:none"> <h3 class="all_title" id="enpatent55">相关主题</h3> <ul id="subject"> </ul> </div> </div> </div> </div> <div class="right rightcon"> <div class="details_img cardcommon clearfix" style="margin-bottom: 10px;display:none;" > </div> </div> </div> <div id="thesis_get_original1" class="downloadBth" style="bottom: 19px;z-index: 999;" onclick="ywcd('0704028162683','4',7,2,1,'',this,24)" class="delivery" prompt="010401" title="通过人工服务将文献原文发送至邮箱" >获取原文</div> <div class="journalsub-pop-up" style="display: none"> <div 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