Advances in the Total Syntheses of Tetraquinane and Tetraquinane-Type Terpenes

doi:10.6023/cjoc202408029

Abstract

Polyquinane is a class of natural products composed of multiple fused five-membered carbocycles. Their unique structures and potential biological activities have attracted the interest of the synthetic community. Among them, the structures with four fused five-membered carbocycles (known as tetraquinane), and those with three five-membered carbocycles fused by one six-membered carbocycle that referred to as tetraquinane-type terpenes, are particularly distinctive. This review provides a chronological overview of the total synthesis efforts of tetraquinane and tetraquinane-type terpenes.

Key words: nature products, polyquinane, tetraquinane, tetraquinane-type terpenes, total synthesis

Cite this article

Yunbo Yang, Hanfeng Ding. Advances in the Total Syntheses of Tetraquinane and Tetraquinane-Type Terpenes[J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 725-747.

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Fig. & Tab. 33

Figure 1. Main skeletal types of polyquinanes and the representative molecules

Figure 2. Teraquinane and teraquinane-type terpenes

Figure 3. Structures of natural products Crinipellins

Scheme 1. Piers’ total synthesis of (±)-Crinipellin B

Scheme 2. Lee’s total synthesis of (–)-Crinipellin A

Scheme 3. [3+2] cycloaddition cascade

Scheme 4. Yang and Gong’s total synthesis of (–)-Crinipellins A and B

Scheme 5. Ding’s total synthesis of (–)-Crinipellins A~F, and (–)-Dihydrocrinipellins A and B (Part I)

Scheme 6. Ding’s total synthesis of (–)-Crinipellins A~F, and (–)-Dihydrocrinipellins A and B (Part II)

Scheme 7. Total synthesis of (–)-Crinipellins A and B by Daiʼs research group

Scheme 8. Two possible ways of the Cargill rearrangement

Figure 4. Structure and biosynthetic pathway of Bipolarolide D (a) and relevant natural products (b)

Scheme 9. Lu’s total synthesis of (–)-Bipolarolide D

Figure 5. Structures of Conidiogenones

Scheme 10. Tu’s total synthesis of (–)-Conidiogenone B、(–)-Conidiogenone and (–)-Conidiogenol

Scheme 11. Snyder’s total synthesis of (–)-Conidiogenone, (–)-Conidiogenol, and (–)-Conidiogenones B~D

Scheme 12. Zhai’s total synthesis of (–)-Conidiogenone B, (–)-Conidiogenone and (–)-Conidiogenol

Scheme 13. Lee’s total synthesis of (–)-Conidiogenones B~F, and (–)-12β-Conidiogenone (Part I)

Scheme 14. Lee’s total synthesis of (–)-Conidiogenones B~F, and (–)-12β-Conidiogenone (Part II)

Figure 6. Structure of (+)-Waihoensene

Scheme 15. Lee’s total synthesis of (±)-Waihoensene

Scheme 16. Yang and Huang’s total synthesis of (+)-Waihoensene

Scheme 17. Snyder’s total synthesis of (+)-Waihoensene

Scheme 18. Gaich’s total synthesis of (±)-Waihoensene

Scheme 19. Gaich’s total synthesis of (+)-Waihoensene

Scheme 20. Tu’s total synthesis of (±)-Waihoensene

Figure 7. Structure of (+)-Aberrarone

Scheme 21. Carreira’s total synthesis of (+)-Aberrarone

Scheme 22. Meyer-Schuster rearrangement/Nazarov/cyclopro- panation/aldol cyclization cascade

Scheme 23. Jia’s total synthesis of (+)-Aberrarone

Figure 8. Structures of Phomopsenes (a), and biosynthesis relationship with Conidiogenones (b)

Scheme 24. Tu and Hou’s total synthesis of (+)-iso-Phomopsene, (–)-Phomopsene and (+)-Methyl Phomopsenonate

Scheme 25. Beckmann fragmentation/recombination

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