Oxidative Alkene Functionalizations via Selenium-π-Acid Catalysis
Oxidative Alkene Functionalizations via Selenium-π-Acid Catalysis
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DOI：
10.1021/acscatal.7b01216
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发表时间：
2017-09-01
期刊：
影响因子：
12.9
通讯作者：
Breder, Alexander
中科院分区：
文献类型：
--
作者：
Ortgies, Stefan;Breder, Alexander
简单非极性烯烃的催化氧化官能化反应是现代化学方法研究领域的关键技术之一。在这种情况下，路易斯酸硒物种经历了一个稳步增长的应用范围在催化氧化的简单烯烃在整个近年来。类似于它们的金属对应物，例如阳离子金和铂络合物，硒离子（即，RSe+）显示出对π键的特殊反应性，这允许烯烃的高度化学选择性亲电官能化。这种独特的反应性特征使得能够开发多种多样的催化键形成过程，例如烯丙基和乙烯基胺化、分子间和分子内缩合、卤化和醚化。与这些方案相关的显著特征是高区域控制，通常温和的反应条件，操作简单，硒催化的烯烃氧化可以进行，和精致的官能团耐受性。这些方面使得硒-π-酸催化对于多官能化分子的后期氧化非常有吸引力，这是一种仍有待充分探索的资产。在这个角度来看，硒-π-酸催化领域的最新贡献被描绘出来，并与以前的方法，机制和理论研究中获得的指示性见解放在一起。
Catalytic oxidative functionalizations of simple, non-polarized alkenes represent one of the lynchpin technologies in the realm of modern methodological chemical research. In this context, Lewis-acidic selenium species have experienced a steadily increasing scope of applications in catalytic oxidations of simple alkenes throughout recent years. In analogy to their metallic counterparts, such as cationic gold and platinum complexes, selenenium ions (i.e., RSe+) display an exceptional reactivity toward pi-bonds, which allows for the highly chemoselective electrophilic functionalization of alkenes. This distinct reactivity profile enabled the development of a diverse array of catalytic bond-forming processes, such as allylic and vinylic aminations, inter- and intramolecular esterifications, halogenations, and etherifications. Remarkable features associated with such protocols are the high regiocontrol, the commonly mild reaction conditions, the operational simplicity by which selenium-catalyzed alkene oxidations can be conducted, and the exquisite functional group tolerance. These aspects make selenium-pi-acid catalysis very attractive for late-stage oxidations of polyfunctionalized molecules, an asset that still remains to be fully explored. In this Perspective, the latest contributions to the field of selenium-pi-acid catalysis are delineated and placed into context with indicatory insights gained from previous methodological, mechanistic, and theoretical studies.