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

末端烯烃的催化抗马尔可夫尼科夫（AM）氧化可提供末端氧官能化的有机化合物。这篇简短的综述主要总结了我们最近在芳族和脂肪族末端烯烃的钯催化AM氧化制得缩醛（氧化缩醛）和醛（瓦克型氧化）方面的最新进展，以及相关报道。这些反应证明了PdCl ₂（MeCN）₂ / CuCl /电子不足的环状烯烃/ O ₂催化体系的功效。值得注意的是，缺电子的环状烯烃，例如p-苯醌（BQs）和马来酰亚胺是关键的添加剂，可促进氧亲核试剂对配位末端烯烃的亲核攻击并增强AM选择性。BQs还可根据反应条件氧化Pd（0）。还讨论了提高AM选择性的其他几个因素，例如亲核试剂的空间需求，缓慢的底物添加和卤素定向基团。

1引言

2芳烃对末端缩醛的抗马尔科夫尼科夫氧化

3芳烃的抗马尔科夫尼科夫氧化法制醛

4脂族烯烃对末端缩醛的抗马尔科夫尼科夫氧化

5脂肪族烯烃对马尔夫的抗马尔科夫尼科夫氧化

六，结论