Total Synthesis of trans-4'a-Methyl-3',4'a,9',10',10'a-hexahydro-spiro[cyclobutane-1,1'(2H)-phenanthrene]

doi:10.6023/cjoc202404026

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (11): 3386-3391.DOI: 10.6023/cjoc202404026 Previous Articles Next Articles

ARTICLE

trans-4'a-Methyl-3',4'a,9',10',10'a-hexahydro-spiro[cyclobutane-1,1'(2H)-phenanthrene]的全合成

戴伟昊, 霍晨雨, 郑天禄, 朱道勇^*(), 王少华^*()

兰州大学药学院功能有机分子化学国家重点实验室兰州 730000

收稿日期:2024-04-18 修回日期:2024-05-26 发布日期:2024-07-02
基金资助:
国家重点研发计划(2023YFA1506404); 甘肃省科技计划(23ZDFA003); 甘肃省科技计划(23JRRA1144); 甘肃省科技计划(23JRRA1028); 甘肃省科技计划(23CXGA0043); 兰州市科技计划(2023-1-17); 兰州市科技计划(2023-QN-18); 中央高校基本科研业务专项(lzujbky-2022-ct03); 中央高校基本科研业务专项(lzujbky-2022-sp09); 中央高校基本科研业务专项(lzujbky-2023-ct02); 中央高校基本科研业务专项(lzujbky-2023-pd08); 陇药协同创新中心和甘肃省药物研发计划(2022GSMPA0010)

Total Synthesis of trans-4'a-Methyl-3',4'a,9',10',10'a-hexahydro-spiro[cyclobutane-1,1'(2H)-phenanthrene]

Weihao Dai, Chenyu Huo, Tianlu Zheng, Daoyong Zhu^*(), Shaohua Wang^*()

School of Pharmacy, State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000

Received:2024-04-18 Revised:2024-05-26 Published:2024-07-02
Contact: *E-mail:wangshh@lzu.edu.cn;zhudy@lzu.edu.cn
Supported by:
National Key R&D Program of China(2023YFA1506404); Science and Technology Program of Gansu Province(23ZDFA003); Science and Technology Program of Gansu Province(23JRRA1144); Science and Technology Program of Gansu Province(23JRRA1028); Science and Technology Program of Gansu Province(23CXGA0043); Lanzhou Science and Technology Planning Project(2023-1-17); Lanzhou Science and Technology Planning Project(2023-QN-18); Fundamental Research Funds for the Central Universities(lzujbky-2022-ct03); Fundamental Research Funds for the Central Universities(lzujbky-2022-sp09); Fundamental Research Funds for the Central Universities(lzujbky-2023-ct02); Fundamental Research Funds for the Central Universities(lzujbky-2023-pd08); Collaborative Innovation Center for Northwestern Chinese Medicine of Lanzhou University and the Drug Research Project of Gansu Province(2022GSMPA0010)

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Abstract

The efficient total synthesis of trans-4'a-methyl-3',4'a,9',10',10'a-hexahydro-spiro[cyclobutane-1,1'(2H)- phenanthrene] has been accomplished starting from commercially available 3-phenylpropanal by two routes which take Au-catalyzed 1,3-acyloxy migration/cyclization cascade and InI₃-catalyzed polyene-type cyclization as the key synthesis steps, respecti- vely.

Key words: trans-4'a-methyl-3',4'a,9',10',10'a-hexahydro-spiro[cyclobutane-1,1'(2H)-phenanthrene], total synthesis, natural product

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Weihao Dai, Chenyu Huo, Tianlu Zheng, Daoyong Zhu, Shaohua Wang. Total Synthesis of trans-4'a-Methyl-3',4'a,9',10',10'a-hexahydro-spiro[cyclobutane-1,1'(2H)-phenanthrene][J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3386-3391.

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Fig. & Tab. 5

Scheme 1. Selected several polycyclic terpenes

Scheme 2. Two polyene cyclization modes

Scheme 3. Retrosynthetic analysis of 1

Scheme 4. Synthetic route 1 of 1 Reaction conditions: (a) CuI, Na2SO3, K2CO3, DBU, 1-ethynylcyclobutan-1-ol, DMF, r.t.; (b) Et2Zn, ZnCl2, Cp2Zr(H)Cl, toluene/THF, r.t.; (c) InI3, DCM, －40 ℃; (d) H2, Pd (10%)/C, 35 ℃.

Scheme 5. Synthetic route 2 of compound 1 Reaction conditions: (e) CuI, Na2SO3, K2CO3, DBU, 1-ethynylcyclobutyl acetate, DMF, r.t.; (f) Au(PPh3)Cl, AgNTf2, toluene, －30 ℃; (g) K2CO3, V(MeOH)∶V(H2O)=10∶1, r.t.; (h) propane-1,3-dithiol, BF3?Et2O, DCM, 0 ℃; (i) H2, Raney-Ni, C2H5OH, reflux.

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trans-4'a-Methyl-3',4'a,9',10',10'a-hexahydro-spiro[cyclobutane-1,1'(2H)-phenanthrene]的全合成

Total Synthesis of trans-4'a-Methyl-3',4'a,9',10',10'a-hexahydro-spiro[cyclobutane-1,1'(2H)-phenanthrene]

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Fig. & Tab. 5

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