Allylic Oxidations in Natural Product Synthesis

Akihiko Nakamura; Masahisa Nakada

doi:10.1055/s-0033-1338426

Synthesis, Table of Contents

Synthesis 2013; 45(11): 1421-1451
DOI: 10.1055/s-0033-1338426

review

Allylic Oxidations in Natural Product Synthesis

Akihiko Nakamura

Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555, Japan Fax: +81(3)52863240 Email: mnakada@waseda.jp

,

Masahisa Nakada*

Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555, Japan Fax: +81(3)52863240 Email: mnakada@waseda.jp

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Abstract

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Abstract

Although C–H oxidation of hydrocarbons is generally difficult, allylic C–H oxidation is relatively simple and predictable, even on a preparative scale, because active species generated at the allylic position are stabilized by the double bond. Therefore, allylic oxidation has been employed in natural product synthesis, and a variety of reagents and conditions for allylic oxidation have been reported. However, reagents and conditions suitable for natural product synthesis are limited in terms of efficiency and chemo-, regio-, and stereoselectivity, owing to the structural and characteristic diversity of natural products. This review addresses allylic oxidations, highlighting reagents and conditions that meet the requirements for natural product synthesis.

1 Introduction

2 Selenium Reagents

2.1 Selenium Dioxide

2.2 Diphenyldiselenide–Iodoxybenzene

3 Chromium(VI) Reagents

3.1 Chromic Acid and Chromate Ester

3.2 Chromium Trioxide–3,5-Dimethylpyrazole (CrO₃·3,5-DMP)

3.3 PCC and PDC

4 Transition-Metal Reagents

5 Others

6 Conclusion

Key words

allylic oxidation - C–H oxidation - natural products - selectivity - total synthesis

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References

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