Progress on the Total Synthesis of Ryania Diterpenoids

doi:10.6023/cjoc202409037

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (3): 804-813.DOI: 10.6023/cjoc202409037 Previous Articles Next Articles

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尼亚那属二萜天然产物的全合成研究进展

孟龙, 乔金宝, 赵玉明^*()

陕西师范大学化学化工学院应用表面与胶体化学教育部重点实验室西安 710119

收稿日期:2024-09-26 修回日期:2024-12-19 发布日期:2025-01-03
基金资助:
国家自然科学基金(22371176); 国家自然科学基金(22201168)

Progress on the Total Synthesis of Ryania Diterpenoids

Long Meng, Jin-Bao Qiao, Yu-Ming Zhao()

Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education (MOE), School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119

Received:2024-09-26 Revised:2024-12-19 Published:2025-01-03
Contact: * E-mail: ymzhao@snnu.edu.cn
Supported by:
National Natural Science Foundation of China(22371176); National Natural Science Foundation of China(22201168)

Ryania diterpene natural products were isolated from Ryania speciosa in the Central/South American, structurally which have a cage-type pentacyclic core, multiple continuous stereocenters, and a high oxidation state. Biological studies have found that its member ryanodine has a specific regulatory effect on myocardial calcium ion channels (PyR). It is one of the few organic small molecule compounds with this function discovered so far and has potential medicinal value for treating cardiovascular diseases. However, the complex chemical structure makes the synthesis of these natural products full of challenges. Herein the current research progress of organic chemists on the total synthesis of these natural products is reviewed.

Key words: ryania diterpenoid, natural product, total synthesis

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Long Meng, Jin-Bao Qiao, Yu-Ming Zhao. Progress on the Total Synthesis of Ryania Diterpenoids[J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 804-813.

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Fig. & Tab. 12

Figure 1. Representative ryania diterpene natural product

Scheme 1. Total synthesis of ryanodol (3)

Scheme 2. Total synthesis of the natural product 3-epi-ryanodol (4)

Scheme 3. Total synthesis of ryanodol (3)

Scheme 4. Total synthesis of ryanodine (1)

Scheme 5. Asymmetric total synthesis of ryanodine (1) and ryanodol (3)

Scheme 6. Total synthesis of the natural products cinncassiols A, B (54, 6), cinnzeylanol (5) and 3-epi-ryanodol (4)

Scheme 7. Asymmetric total synthesis of (+)-ryanodol (3)

Scheme 8. Asymmetric total synthesis of natural products (+)-ryanodine (1) and (+)-20-deoxyspiganthine (8)

Scheme 9. Total synthesis of anhydroryanodol (20)

Scheme 10. Total synthesis of garajonone (7)

项目	课题组	天然产物	关键步骤
1	Deslongchamps	(+)-Ryanodol (3), 3-epi-ryanodol (4)	分子间的Diels-Alder反应、氧化裂解/跨环的Aldol反应
2	Inoue	(+)-Ryanodine (1), (+)-ryanodol (3), 3-epi-ryanodol (4), cinnzeylanol (5), cinncassiols B (6), cinncassiols A (51)	自由基介导的C—C/C—O的偶联反应、RCM反应
3	Reisman	(+)-Ryanodine (1), (+)-ryanodol (3), (+)-20-deoxyspiganthine (8)	Pauson-Khand成环反应、二氧化硒介导的选择性氧化反应
4	Micalizio	Ryanodol (3)	钛介导的炔烃与1,3-二羰基分子内立体选择性的偶联反应
5	赵玉明	Garajonone (7)	钯催化Heck/插羰串联环化反应、氧化去芳构化、熔金属还原环化反应

Table 1. Progress in total synthesis of natural products of Ryania Diterpenoids

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尼亚那属二萜天然产物的全合成研究进展

Progress on the Total Synthesis of Ryania Diterpenoids

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