Synthesis of Polycyclic Frameworks through Iron-Catalyzed Intramolecular [5+2] Cycloaddition

Yongjiang Liu; Yanhui Zhang; Xiao Wang; Shaomin Fu; Bo Liu

doi:10.1055/s-0037-1610258

Synlett, Inhaltsverzeichnis

Synlett 2018; 29(15): 1978-1982
DOI: 10.1055/s-0037-1610258

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Synthesis of Polycyclic Frameworks through Iron-Catalyzed Intramolecular [5+2] Cycloaddition

Yongjiang Liu

Key Laboratory of Green Chemistry &Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China eMail: chembliu@scu.edu.cn eMail: fsm09@aliyun.com

,

Yanhui Zhang

Key Laboratory of Green Chemistry &Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China eMail: chembliu@scu.edu.cn eMail: fsm09@aliyun.com

,

Xiao Wang

Key Laboratory of Green Chemistry &Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China eMail: chembliu@scu.edu.cn eMail: fsm09@aliyun.com

,

Shaomin Fu*

Key Laboratory of Green Chemistry &Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China eMail: chembliu@scu.edu.cn eMail: fsm09@aliyun.com

,

Bo Liu *

Key Laboratory of Green Chemistry &Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. of China eMail: chembliu@scu.edu.cn eMail: fsm09@aliyun.com

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Abstract

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Abstract

A concise and efficient approach to the core of the C₁₈/C₁₉ diterpenoid alkaloids and phomopsterone B is reported. Both syntheses share the same iron-catalyzed intramolecular [5+2] cycloaddition to assemble the tricyclo[6.3.1.0^1,6]]dodecane skeleton. The following approach to the 6/5/6/7 tetracyclic core scaffold of C₁₈/C₁₉ diterpenoid alkaloids features a regioselective Grignard addition/thermal Claisen rearrangement/RCM cyclization. Meanwhile the synthetic steps to access the spiro 6/5/6 tricyclic subunits of phomopsterone B were characterized as intramolecular aldol reaction, Wacker oxidation, and Criegee reaction.

Key words

C₁₈/C₁₉-diterpenoid alkaloids - phomopsterone B - Iron-catalyzed - [5+2] cycloaddition

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Referenzen

References and Notes
1 Wang F.-P. Chen Q.-H. Liang X.-T. In The Alkaloids: Chemistry and Biology . Vol. 67. Cordell GA. Elsevier Science; New York: 2009: 1-78

2a Wang F.-P. Chen Q.-H.. in The Alkaloids: Chemistry and Biology . Vol. 69. Cordell GA. Elsevier Science; New York: 2010: 1-577
2b Guo R. Guo C. He D. Zhao D. Shen Y. Chin. J. Chem. 2017; 35: 1644

3a Usmanova SK. Tel’nov VA. Yunusov MS. Abdullaev ND. Shreter AI. Filippova GB. Khim. Prir. Soedin. 1987; 23: 879
3b Tel’nov VA. Yunusov MS. Abdullaev ND. Zhamierashvili MG. Khim. Prir. Soedin. 1988; 24: 556
3c Shi X.-W. Lu Q.-Q. Zhou J.-H. Cui X.-A. Acta Cryst. 2015; E71: 550

4 Dzhakhangirov FN. Sultankhodzhaev MN. Tashkhodzhaev B. Salimov BT. Chem. Nat. Compd. 1997; 33: 190
5 Zhang HQ. Zhu YL. Zhu RH. Acta Bot. Sin. 1982; 24: 259

6a Wiesner K. Tsai TY. R. Huber K. Bolton SE. Vlahov R. J. Am. Chem. Soc. 1974; 96: 4990
6b Wiesner K. Pure Appl. Chem. 1975; 41: 93
6c Wiesner K. Tsai TY. R. Nambiar KP. Can. J. Chem. 1978; 56: 1451
6d Wiesner K. Pure Appl. Chem. 1979; 51: 689

7 Shi Y. Wilmot JT. Nordstrøm LU. Tan DS. Gin DY. J. Am. Chem. Soc. 2013; 135: 14313

8a Marth CJ. Gallego GM. Lee JC. Lebold TP. Kulyk S. Kou KG. M. Qin J. Lilien R. Sarpong R. Nature 2015; 528: 493
8b Kou KG. M. Kulyk S. Marth CJ. Lee JC. Doering NA. Li BX. Gallego GM. Lebold TP. Sarpong R. J. Am. Chem. Soc. 2017; 139: 13882

9a Nishiyama Y. Yokoshima S. Fukuyama T. Org. Lett. 2016; 18: 2359
9b Nishiyama Y. Yokoshima S. Fukuyama T. Org. Lett. 2017; 19: 5833

For recent review articles, see:

10a Wang F.-P. Chen Q.-H. Liu X.-Y. Nat. Prod. Rep. 2010; 27: 529
10b Hamlin AM. Kisunzu JK. Sarpong R. Org. Biomol. Chem. 2014; 12: 1846
10c Zhu G. Liu R. Liu B. Synthesis 2015; 47: 2691
10d Liu X.-Y. Qin Y. Asian J. Org. Chem. 2015; 4: 1010

For selected research work published recently, see:

11a Mei R.-H. Liu Z.-G. Cheng H. Xu L. Wang F.-P. Org. Lett. 2013; 15: 2206
11b Cheng H. Zeng F.-H. Ma D. Jiang M.-L. Xu L. Wang F.-P. Org. Lett. 2014; 16: 2299
11c Jiang M.-L. Meng Y.-J. Xiong W.-Y. Xu L. Tetrahedron Lett. 2016; 57: 1610
11d Tabuchi T. Urabe D. Inoue M. J. Org. Chem. 2016; 81: 10204
11e Hagiwara K. Tabuchi T. Urabe D. Inoue M. Chem. Sci. 2016; 7: 4372
11f Zhu M. Li X. Song X. Wang Z. Liu X. Song H. Zhang D. Wang F.-P. Qin Y. Chin. J. Chem. 2017; 35: 991
11g Minagawa K. Urabe D. Inoue M. J. Antibiot. 2018; 71: 326
11h Liu M. Cheng C. Xiong W. Cheng H. Wang J.-L. Xu L. Org. Chem. Front. 2018; 5: 1502

12a Hu Z. Wu Y. Xie S. Sun W. Guo Y. Li X.-N. Liu J. Li H. Wang J. Luo Z. Xue Y. Zhang Y. Org. Lett. 2017; 19: 258
12b Amagata T. Tanaka M. Yamada T. Doi M. Minoura K. Ohishi H. Yamori T. Numata A. J. Nat. Prod. 2007; 70: 1731

13a Janardhanam S. Shanmugam P. Rajagopalan K. J. Org. Chem. 1993; 58: 7782
13b Shanmugam P. Srinivasan R. Rajagopalan K. Tetrahedron 1997; 53: 6085

14 Matsuo J. Sasaki S. Hoshikawa T. Ishibashi H. Chem. Commun. 2010; 934
15 Rinderhagen H. Mattay J. Chem. Eur. J. 2004; 10: 851
16 Liu Y. Wang X. Chen S. Fu S. Liu B. Org. Lett. 2018; 20: 2934
17 Nicolaou KC. Dong L. Deng L. Talbot AC. Chen DY.-K. Chem. Commun. 2010; 70

18a Hanessian S. Vakiti RR. Dorich S. Banerjee S. Lecomte F. DelValle JR. Zhang J. Deschênes-Simard B. Angew. Chem. Int. Ed. 2011; 50: 3497
18b Hanessian S. Vakiti RR. Dorich S. Banerjee S. Lecomte Deschênes-Simard B. J. Org. Chem. 2012; 77: 9458

19 We also tried to construct the 6/5/6/5 tetracyclic core skeleton of the C₁₈/C₁₉-diterpenoid alkaloids, but failed (Scheme 5).
20 Reduction of compound 10 under LiAlH₄ gave two diastereoisomers, 20-1 and 20-2 in 49% yield and 24% yield, respectively. Compound 20-1 was further transformed into compound 20, the structure of which was confirmed by X-ray crystallography. The stereochemistry of hydroxyl group at C1 in target compound 11 could be identified from X-ray crystallographic analysis of compound 20 (Scheme 6).
21 Shen J. Shi Y. Tian W. Chin. J. Chem. 2015; 33: 683
22 Experimental Procedure and Characteristic Data for Ketone (24): Compound 21 (22.3 mg, 0.08 mmol) was added to toluene (0.5 mL) in a sealed tube and stirred at 170 °C overnight. The solvent was then removed in vacuo to afford the crude product, which was used in the next step without further purification. To a solution of Grubbs II (17.5 mg, 0.02 mmol) in CH₂Cl₂ (8.0 mL) at room temperature was added the above product in CH₂Cl₂ (2.5 mL) and the mixture was stirred at room temperature for 10 h. The solvent was then removed in vacuo and the crude product was purified by column chromatography (EtOAc/petroleum ether = 1:5) to afford the product 24 (12.1 mg, 60% for two steps) as a white solid; mp 119–121 °C. ¹H NMR (400 MHz, CDCl₃): δ = 5.65–5.59 (m, 2 H), 3.87 (s, 1 H), 2.88 (t, J = 5.2 Hz, 1 H), 2.73–2.60 (m, 2 H), 2.46 (dd, J = 5.2, 7.2 Hz, 1 H), 2.04–1.98 (m, 2 H), 1.90–1.81 (m, 2 H), 1.70 (dd, J = 5.2, 13.2 Hz, 1 H), 1.66–1.59 (m, 1 H), 1.52–1.47 (m, 1 H), 1.42 (ddd, J = 2.8, 7.6, 14.0 Hz, 1 H), 1.15 (dddd, J = 2.8, 4.0, 12.4, 25.2 Hz, 1 H), 1.03 (ddt, J = 2.8, 12.8, 25.6 Hz, 1 H), 0.72 (ddd, J = 3.2, 13.2, 25.6 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 211.8, 211.0, 132.7, 127.9, 78.9, 60.5, 50.6, 48.5, 35.2, 34.8, 31.6, 30.6, 24.0, 22.7, 20.6. IR (neat): 2925, 2850, 1735, 1448, 1369, 1239, 1141, 1030 cm^–1. HRMS (ESI): m/z [M+Na]⁺ calcd for C₁₅H₁₈NaO₃: 269.1154; found: 269.1151.

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