Synthesis 2021; 53(05): 848-860
DOI: 10.1055/s-0040-1706570
short review

Palladium-Catalyzed Anti-Markovnikov Oxidation of Aromatic and Aliphatic Alkenes to Terminal Acetals and Aldehydes

Yasuyuki Ura
This study was supported by the Japan Society for the Promotion of Science (JSPS) (KAKENHI) [Grant Nos. JP16H01028 (in Precisely Designed Catalysts with Customized Scaffolding), JP23750112, JP25410116, JP18K05122, and JP18H03914], and by The Society of Synthetic Organic Chemistry, Japan (Asahi Kasei Pharma Award).


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



Publication History

Received: 31 August 2020

Accepted after revision: 13 October 2020

Publication Date:
12 November 2020 (online)

© 2020. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
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