Palladium-Catalyzed Anti-Markovnikov Oxidation of Aromatic and Aliphatic Alkenes to Terminal Acetals and Aldehydes
Palladium-Catalyzed Anti-Markovnikov Oxidation of Aromatic and Aliphatic Alkenes to Terminal Acetals and Aldehydes
复制标题
DOI：
10.1055/s-0040-1706570
复制
发表时间：
2020-11
期刊：
影响因子：
--
通讯作者：
Y. Ura
中科院分区：
文献类型：
--
作者：
Y. Ura
摘要末端烯烃的催化反马尔可夫尼科夫(AM)氧化反应可以得到末端含氧官能化的有机化合物。本文主要综述了Pd催化AM氧化芳香族和脂肪族末端烯烃得到末端缩醛(氧化缩醛)和末端醛(Wacker-型氧化)的最新进展，以及相关报道。这些反应证明了PdCl2(MeCN)2/CuCl2/缺电子环烯烃/O2催化体系的有效性。值得注意的是，缺乏电子的环烯烃如对苯二酚(BQS)和马来酰亚胺是促进氧亲核试剂对配位末端烯烃的亲核攻击并提高AM选择性的关键添加剂。根据反应条件，BQS还具有氧化Pd(0)的功能。还讨论了其它几个提高AM选择性的因素，如亲核试剂的空间需求、底物的缓慢加成和卤素导向基团。1引言2芳烃反Markovnikov氧化制末端缩醛3反Markovnikov氧化制醛4反Markovnikov氧化制末端缩醛5反Markovnikov氧化制醛6结论
Abstract Catalytic anti-Markovnikov (AM) oxidation of terminal alkenes can provide terminally oxyfunctionalized organic compounds. This short review mainly summarizes our recent progress on the Pd-catalyzed AM oxidations of aromatic and aliphatic terminal alkenes to give terminal acetals (oxidative acetalization) and aldehydes (Wacker-type oxidation), along with related reports. These reactions demonstrate the efficacy of the PdCl2(MeCN)2/CuCl/electron-deficient cyclic alkenes/O2 catalytic system. Notably, electron-deficient cyclic alkenes such as p-benzoquinones (BQs) and maleimides are key additives that facilitate nucleophilic attack of oxygen nucleophiles on coordinated terminal alkenes and enhance the AM selectivity. BQs also function to oxidize Pd(0) depending on the reaction conditions. Several other factors that improve the AM selectivity, such as the steric demand of the nucleophiles, slow substrate addition, and halogen-directing groups, are also discussed. 1 Introduction 2 Anti-Markovnikov Oxidation of Aromatic Alkenes to Terminal Acetals 3 Anti-Markovnikov Oxidation of Aromatic Alkenes to Aldehydes 4 Anti-Markovnikov Oxidation of Aliphatic Alkenes to Terminal Acetals 5 Anti-Markovnikov Oxidation of Aliphatic Alkenes to Aldehydes 6 Conclusion