Baeyer-Villiger oxidation: a promising tool for the synthesis of natural products: a review

Abstract

Baeyer-Villiger oxidation is a well-known reaction utilized for the synthesis of lactones and ester functionalities from ketones. Chiral lactones can be synthesized from chiral or racemic ketones by employing asymmetric Baeyer-Villiger oxidation. These lactones act as key intermediates in the synthesis of most of the biologically active natural products, their analogues, and derivatives. Various monooxygenases and oxidizing agents facilitate BV oxidation, providing a broad range of synthetic applications in organic chemistry. The variety of enzymatic and chemoselective Baeyer-Villiger oxidations and their substantial role in the synthesis of natural products i.e., alkaloids, polyketides, fatty acids, terpenoids, etc. (reported since 2018) have been summarized in this review article.

Scheme 1. General mechanism of Baeyer–Villiger oxidation.

Fig. 1. Structures of a few biologically active natural products synthesized by BVO.

Fig. 2. Pictorial representation of alkaloid-based natural products synthesized by Baeyer–Villiger oxidation reaction.

Scheme 2. Synthesis of homoproaporphine alkaloids; jolantidine 13, regelinine 15, and kesselringine 18via Baeyer–Villiger oxidation.

Scheme 3. Synthesis of (−)-misramine 26via Baeyer–Villiger oxidation.

Scheme 4. Synthesis of glycosylated derivatives of Lamellarin D 31via Baeyer–Villiger oxidation.

Scheme 5. Synthesis of cyanogramides B 38 and C 39via Baeyer–Villiger oxidation.

Scheme 6. Synthesis of psammaplysin A 44via Baeyer–Villiger oxidation.

Scheme 7. Synthesis of deoxypsammaplysins O 54b, K 55 and deoxyceratinamide A 55via Baeyer–Villiger oxidation.

Scheme 8. Synthesis of natural marine alkaloids; psammaplysins 65 and 67via Baeyer–Villiger oxidation.

Scheme 9. Synthesis of metaphanine 76 and oxoepistiphemiersine 77via Baeyer–Villiger oxidation.

Fig. 3. Structures of some naturally occurring polyketides synthesized via Baeyer–Villiger oxidation.

Scheme 10. Synthesis of (−)-rasfonin 82via Baeyer–Villiger oxidation.

Scheme 11. Synthesis of C_1–792 and C_8–1594 subunits of (+)-discodermolide via Baeyer–Villiger oxidation.

Scheme 12. Synthesis of C_15–21101 and C_9–13103 subunits of (+)-discodermolide via Baeyer–Villiger oxidation.

Scheme 13. Synthesis of vertinolide 108 and Plakinidone B 111via Baeyer–Villiger oxidation.

Scheme 14. Synthesis of acremolactone B 121via Baeyer–Villiger oxidation.

Fig. 4. Pictorial framework elaborating the structures of some terpene-based natural products obtained by involving BVO as a key step.

Scheme 15. Synthesis of friedelanes 123 and 124via Baeyer–Villiger oxidation.

Scheme 16. Synthesis of anhydroryanodol 132via Baeyer–Villiger oxidation.

Scheme 17. Synthesis of zealactone 137via Baeyer–Villiger oxidation.

Scheme 18. Synthesis of propindilactone G 146via Baeyer–Villiger oxidation.

Scheme 19. Synthesis of euonyminol 152via Baeyer–Villiger oxidation.

Scheme 20. Synthesis of asnovoline A 158 and E 159via Baeyer–Villiger oxidation.

Fig. 5. Fatty acid-based natural products synthesized by involving BVO as a key step.

Scheme 21. Synthesis of prostaglandin 4via Baeyer–Villiger oxidation.

Scheme 22. Synthesis of thromboxane B₂172via Baeyer–Villiger oxidation.

Fig. 6. Miscellaneous natural products synthesized by involving BVO as a key step.

Scheme 23. Synthesis of nepetoidin B 175via Baeyer–Villiger oxidation.

Scheme 24. Synthesis of protoanemonin 179via Baeyer–Villiger oxidation.

Scheme 25. Synthesis of terfestatin A 186 and terfestatin B 189via Baeyer–Villiger oxidation.

Scheme 26. Synthesis of protease inhibitor; darunavir 2via Baeyer–Villiger oxidation.

Scheme 27. Synthesis of eupomatilones 204 and 205via Baeyer–Villiger oxidation.

Scheme 28. Biosynthesis of benzoquinone 209via Baeyer–Villiger oxidation.

Fig. 7. Pictorial representation of role of BVO in biosynthesis.

Scheme 29. Synthesis of bohemamines 212 and 214 (a–c) via Baeyer–Villiger oxidation.

Scheme 30. Synthesis of testosterone 216 and testololactone 3via Baeyer–Villiger oxidation.

Scheme 31. Synthesis of asperaculin A 220 and penifulvin D 222via Baeyer–Villiger oxidation.

Scheme 32. Synthesis of chartreusin 227via Baeyer–Villiger oxidation.

Scheme 33. Synthesis of secalonic acid (B, D and F) 231via Baeyer–Villiger oxidation.

Scheme 34. Synthesis of vibralactone 236via Baeyer–Villiger oxidation.