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Regioselective Arene C?H Alkylation Enabled by Organic Photoredox Catalysis

机译:通过有机光致毒性催化使能芳烃C'H烷基化。

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Abstract > Expanding the toolbox of C?H functionalization reactions applicable to the late‐stage modification of complex molecules is of interest in medicinal chemistry, wherein the preparation of structural variants of known pharmacophores is a key strategy for drug development. One manifold for the functionalization of aromatic molecules utilizes diazo compounds and a transition‐metal catalyst to generate a metallocarbene species, which is capable of direct insertion into an aromatic C?H bond. However, these high‐energy intermediates can often require directing groups or a large excess of substrate to achieve efficient and selective reactivity. Herein, we report that arene cation radicals generated by organic photoredox catalysis engage in formal C?H functionalization reactions with diazoacetate derivatives, furnishing sp 2 –sp 3 coupled products with moderate‐to‐good regioselectivity. In contrast to previous methods utilizing metallocarbene intermediates, this transformation does not proceed via a carbene intermediate, nor does it require the presence of a transition‐metal catalyst. </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> > 扩展适用于复杂分子的后期修饰的C的工具箱是药物化学的感兴趣,其中已知药物的结构变体的制备是药物发育的关键策略。用于芳族分子的官能化的一种歧管利用重氮化合物和过渡金属催化剂产生金属甲苯物质,其能够将其直接插入芳族C-H键。然而,这些高能量中间体通常需要引导基团或大量过量的基材以获得有效和选择性的反应性。在此,我们报告称,通过有机摄影氧化氧催化在正式的C-H官能化反应中产生的芳烃阳离子自由基与二氮酸酯衍生物,提供SP 2 </ sup> -sp. 3 </ sup> 耦合产品,具有中等至良好的区域选择性。与先前的使用金属甲苯中间体的方法相比,该转化不会通过卡宾中间体进行,也不需要存在过渡金属催化剂。 </ 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5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=Holmberg‐Douglas Natalie&option=202" target="_blank" rel="nofollow">Holmberg‐Douglas Natalie;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Onuska Nicholas P. R.&option=202" target="_blank" rel="nofollow">Onuska Nicholas P. R.;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Nicewicz David A.&option=202" target="_blank" rel="nofollow">Nicewicz David A.;</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 North Carolina at Chapel HillChapel Hill NC 27599-3290 USA;</p> <p>Department of ChemistryUniversity of North Carolina at Chapel HillChapel Hill NC 27599-3290 USA;</p> <p>Department of ChemistryUniversity of North Carolina at Chapel HillChapel Hill NC 27599-3290 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=alkylation&option=203" rel="nofollow">alkylation;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=arenes&option=203" rel="nofollow">arenes;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=diazo compounds&option=203" rel="nofollow">diazo compounds;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=organic photoredox catalysis&option=203" rel="nofollow">organic photoredox catalysis;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=synthetic methods&option=203" rel="nofollow">synthetic methods;</a> </p> <div class="translation"> 机译:烷基化;arenes;重氮化合物;有机摄影氧催化;合成方法; </div> </li> </ul> </div> </div> <div class="literature cardcommon"> <div class="similarity "> <h3 class="all_title" id="enpatent66">相似文献</h3> <div class="similaritytab clearfix"> <ul> <li class="active" >外文文献</li> <li >中文文献</li> <li >专利</li> </ul> </div> <div class="similarity_details"> <ul > <li> <div> <b>1. </b><a class="enjiyixqcontent" href="/journal-foreign-detail/0704028162556.html">Regioselective Arene C?H Alkylation Enabled by Organic Photoredox Catalysis</a> <b>[J]</b> . <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Holmberg‐Douglas Natalie&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">Holmberg‐Douglas Natalie,</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Onuska Nicholas P. 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