Enantioselective Synthesis of Bicyclo[3.2.1]octadienes via Palladium-Catalyzed Intramolecular Alkene-Alkyne Coupling Reaction
Qiuyu Li
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
These authors contributed equally to this work.
Search for more papers by this authorJiajia Li
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
These authors contributed equally to this work.
Search for more papers by this authorJie Zhang
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
Search for more papers by this authorShu Wu
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
Search for more papers by this authorYu Zhang
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Aijun Lin
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Hequan Yao
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
Search for more papers by this authorQiuyu Li
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
These authors contributed equally to this work.
Search for more papers by this authorJiajia Li
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
These authors contributed equally to this work.
Search for more papers by this authorJie Zhang
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
Search for more papers by this authorShu Wu
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
Search for more papers by this authorYu Zhang
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Aijun Lin
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Hequan Yao
State Key Laboratory of Natural Medicines (SKLNM), Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, Nanjing, 210009 P. R. China
Search for more papers by this authorAbstract
Bicyclo[3.2.1]octadiene compounds and derivatives exist in a number of natural products and bioactive compounds. Nevertheless, catalytic enantioselective protocols for the synthesis of these skeletons have not been disclosed. Herein we reported a palladium-catalyzed asymmetric intramolecular alkene-alkyne coupling of alkyne-tethered cyclopentenes, affording a library of enantionenriched bicyclo[3.2.1]octadienes in excellent yields and enantioselectivities (mostly >99 % ee). Moreover, the products could undergo an unusual iodination-induced 1,2-acyl migration, forming iodinated bicyclo[3.2.1]octadienes with three vicinal stereocenters. The enone and isolated olefin motifs embedded in the products provide useful handles for downstream elaboration.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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References
- 1
- 1aZ. Chen, M. L. Trudell, Chem. Rev. 1996, 96, 1179–1193;
- 1bL. N. Mander, Nat. Prod. Rep. 2003, 20, 49–69;
- 1cJ. Y. W. Mak, R. H. Pouwer, C. M. Williams, Angew. Chem. Int. Ed. 2014, 53, 13664–13688.
- 2For selected reviews, see:
- 2aW. Zhao, Chem. Rev. 2010, 110, 1706–1745;
- 2bM. Ruiz, P. López-Alvarado, G. Giorgi, J. C. Menéndez, Chem. Soc. Rev. 2011, 40, 3445–3454;
- 2cJ. Liu, X. Liu, J. Wu, C.-C. Li, Chem. 2020, 6, 579–615;
- 2dL. Min, X. Liu, C.-C. Li, Acc. Chem. Res. 2020, 53, 703–718; for selected examples, see:
- 2eY. Xu, Q. Sun, T.-D. Tan, M.-Y. Yang, P. Yuan, S.-Q. Wu, X. Lu, X. Hong, L.-W. Ye, Angew. Chem. Int. Ed. 2019, 58, 16252–16259;
- 2fJ. Chen, Y. Wang, Z. Ding, W. Kong, Nat. Commun. 2020, 11, 1882;
- 2gX. Mu, H. Yu, H. Peng, W. Xiong, T. Wu, W. Tang, Angew. Chem. Int. Ed. 2020, 59, 8143–8147;
- 2hQ. Wei, J. Cai, X.-D. Hu, J. Zhao, H. Cong, C. Zheng, W.-B. Liu, ACS Catal. 2020, 10, 216–224;
- 2iX.-Y. Huang, P.-P. Xie, L.-M. Zou, C. Zheng, S.-L. You, J. Am. Chem. Soc. 2023, 145, 11745–11753.
- 3
- 3aM. T. Knowe, M. W. Danneman, S. Sun, M. Pink, J. N. Johnston, J. Am. Chem. Soc. 2018, 140, 1998–2001;
- 3bZ. Yuan, Z. Feng, Y. Zeng, X. Zhao, A. Lin, H. Yao, Angew. Chem. Int. Ed. 2019, 58, 2884–2888;
- 3cZ. Yuan, Y. Zeng, Z. Feng, Z. Guan, A. Lin, H. Yao, Nat. Commun. 2020, 11, 2544;
- 3dS. Li, Z. Li, M. Li, L. He, X. Zhang, H. Lv, Nat. Commun. 2021, 12, 5279;
- 3eG. Wang, J.-C. Li, Y.-G. Zhou, Z.-S. Ye, Org. Lett. 2021, 23, 802–807.
- 4For selected reviews:
- 4aB. M. Trost, Acc. Chem. Res. 1990, 23, 34–42;
- 4bI. J. S. Fairlamb, Angew. Chem. Int. Ed. 2004, 43, 1048–1052;
- 4cV. Michelet, P. Y. Toullec, J.-P. Genêt, Angew. Chem. Int. Ed. 2008, 47, 4268–4315;
- 4dA. Marinetti, H. Jullien, A. Voituriez, Chem. Soc. Rev. 2012, 41, 4884–4908;
- 4eI. D. G. Watson, F. D. Toste, Chem. Sci. 2012, 3, 2899–2919;
- 4fC. I. Stathakis, P. L. Gkizis, A. L. Zografos, Nat. Prod. Rep. 2016, 33, 1093–1117; for selected examples, see:
- 4gG. Hilt, J. Treutwein, Angew. Chem. Int. Ed. 2007, 46, 8500–8502;
- 4hB. M. Trost, J. J. Cregg, J. Am. Chem. Soc. 2015, 137, 620–623;
- 4iB. M. Trost, J. J. Cregg, C. Hohn, W.-J. Bai, G. Zhang, J. S. Tracy, Nat. Chem. 2020, 12, 629–637;
- 4jB. M. Trost, G. Zhang, J. Am. Chem. Soc. 2020, 142, 7312–7316.
- 5For selected examples on chiral cyclic compounds:
- 5aB. M. Trost, D. C. Lee, F. Rise, Tetrahedron Lett. 1989, 30, 651–654;
- 5bB. M. Trost, B. A. Czeskis, Tetrahedron Lett. 1994, 35, 211–214;
- 5cA. Goeke, M. Sawamura, R. Kuwano, Y. Ito, Angew. Chem. Int. Ed. Engl. 1996, 35, 662–663;
- 5dP. Cao, X. Zhang, Angew. Chem. Int. Ed. 2000, 39, 4104–4106;
10.1002/1521-3773(20001117)39:22<4104::AID-ANIE4104>3.0.CO;2-X CAS PubMed Web of Science® Google Scholar
- 5eM. Hatano, M. Terada, K. Mikami, Angew. Chem. Int. Ed. 2001, 40, 249–253;
10.1002/1521-3773(20010105)40:1<249::AID-ANIE249>3.0.CO;2-X CAS PubMed Web of Science® Google Scholar
- 5fA. Lei, M. He, X. Zhang, J. Am. Chem. Soc. 2002, 124, 8198–8199;
- 5gM. Hatano, M. Yamanaka, K. Mikami, Eur. J. Org. Chem. 2003, 2552–2555;
- 5hM. Hatano, K. Mikami, J. Am. Chem. Soc. 2003, 125, 4704–4705;
- 5iA. Martínez, P. García-García, M. A. Fernández-Rodríguez, F. Rodríguez, R. Sanz, Angew. Chem. Int. Ed. 2010, 49, 4633–4637;
- 5jS. Yu, C. Wu, S. Ge, J. Am. Chem. Soc. 2017, 139, 6526–6529;
- 5kC. Wu, N. Yoshikai, Angew. Chem. Int. Ed. 2018, 57, 6558–6562;
- 5lC. Wang, S. Ge, J. Am. Chem. Soc. 2018, 140, 10687–10690;
- 5mY.-E. You, S. Ge, Angew. Chem. Int. Ed. 2021, 60, 12046–12052;
- 5nR.-X. Liang, L.-J. Song, J.-B. Lu, W.-Y. Xu, C. Ding, Y.-X. Jia, Angew. Chem. Int. Ed. 2021, 60, 7412–7417;
- 5oS. Gao, C. Wang, J. Yang, J. Zhang, Nat. Commun. 2023, 14, 1301.
- 6For examples on enantioenriched functional 1,4-dienes, see:
- 6aD. Zhang, M. Li, J. Li, A. Lin, H. Yao, Nat. Commun. 2021, 12, 6627;
- 6bZ.-X. Wang, P.-C. Gao, E.-Z. Lin, B.-J. Li, Angew. Chem. Int. Ed. 2022, 61, e202200075.
- 7
- 7aQ. Li, X. Fang, R. Pan, H. Yao, A. Lin, J. Am. Chem. Soc. 2022, 144, 11364–11376;
- 7bM. Cai, J. Ma, Q. Wu, A. Lin, H. Yao, Org. Lett. 2022, 24, 8791–8795;
- 7cQ. Li, Y. Zhang, P. Liu, J. Zhong, B. Gong, H. Yao, A. Lin, Angew. Chem. Int. Ed. 2023, 62, e202211988.
- 8For selected reviews, see:
- 8aM.-H. Filippini, J. Rodriguez, Chem. Rev. 1999, 99, 27–76;
- 8bM. Presset, Y. Coquerel, J. Rodriguez, Chem. Rev. 2013, 113, 525–595;
- 8cK. Gao, J. Hu, H. Ding, Acc. Chem. Res. 2021, 54, 875–889.
- 9
- 9aM. Brookhart, B. Grant, A. F. Volpe Jr, Organometallics 1992, 11, 3920–3922;
- 9bI. Krossing, I. Raabe, Angew. Chem. Int. Ed. 2004, 43, 2066–2090.
- 10Deposition numbers 2232143 (for 2 b), 2268999 (for 4), 2285118 (for 5), 2285119 (for 8), and 2290225 (for 10) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service.
- 11For selected review, see:
- 11aG. Li, X. Huo, X. Jiang, W. Zhang, Chem. Soc. Rev. 2020, 49, 2060–2118; for selected examples, see:
- 11bI. D. Hills, G. C. Fu, J. Am. Chem. Soc. 2004, 126, 13178–13179;
- 11cT. Kochi, T. Hamasaki, Y. Aoyama, J. Kawasaki, F. Kakiuchi, J. Am. Chem. Soc. 2012, 134, 16544–16547;
- 11dJ. Liu, K. Dong, R. Franke, H. Neumann, R. Jackstell, M. Beller, J. Am. Chem. Soc. 2018, 140, 10282–10288;
- 11eS.-Z. Nie, R. T. Davison, V. M. Dong, J. Am. Chem. Soc. 2018, 140, 16450–16454;
- 11fY.-C. Wang, Z.-X. Xiao, M. Wang, S.-Q. Yang, J.-B. Liu, Z.-T. He, Angew. Chem. Int. Ed. 2023, 62, e202215568.
- 12For selected examples, see:
- 12aB. M. Trost, A. C. Gutierrez, E. M. Ferreira, J. Am. Chem. Soc. 2010, 132, 9206–9218;
- 12bA. Mekareeya, P. R. Walker, A. Couce-Rios, C. D. Campbell, A. Steven, R. S. Paton, E. A. Anderson, J. Am. Chem. Soc. 2017, 139, 10104–10114.
- 13For selected examples, see:
- 13aM. Pawliczek, T. F. Schneider, C. Maaß, D. Stalke, D. B. Werz, Angew. Chem. Int. Ed. 2015, 54, 4119–4123;
- 13bD. A. Petrone, I. Franzoni, J. Ye, J. F. Rodríguez, A. I. Poblador-Bahamonde, M. Lautens, J. Am. Chem. Soc. 2017, 139, 3546–3557;
- 13cJ. F. Rodríguez, K. I. Burton, I. Franzoni, D. A. Petrone, I. Scheipers, M. Lautens, Org. Lett. 2018, 20, 6915–6919;
- 13dM. Dong, L. Qi, J. Qian, S. Yu, X. Tong, J. Am. Chem. Soc. 2023, 145, 1973–1981.
- 14For selected reviews, see:
- 14aZ.-L. Song, C.-A. Fan, Y.-Q. Tu, Chem. Rev. 2011, 111, 7523–7556;
- 14bB. M. Wang, Y.-Q. Tu, Acc. Chem. Res. 2011, 44, 1207–1222;
- 14cX.-M. Zhang, Y.-Q. Tu, F.-M. Zhang, Z.-H. Chen, S.-H. Wang, Chem. Soc. Rev. 2017, 46, 2272–2305;
- 14dW.-Z. Weng, B. Zhang, Chem. Eur. J. 2018, 24, 10934–10947;
- 14eX.-M. Zhang, B.-S. Li, S.-H. Wang, K. Zhang, F.-M. Zhang, Y.-Q. Tu, Chem. Sci. 2021, 12, 9262–9274; for selected examples, see:
- 14fZ.-M. Chen, Q.-W. Zhang, Z.-H. Chen, H. Li, Y.-Q. Tu, F.-M. Zhang, J.-M. Tian, J. Am. Chem. Soc. 2011, 133, 8818–8821;
- 14gF. Romanov-Michailidis, L. Guénée, A. Alexakis, Angew. Chem. Int. Ed. 2013, 52, 9266–9270;
- 14hJ. Xie, Z. Zheng, X. Liu, N. Zhang, S. Choi, C. He, G. Dong, J. Am. Chem. Soc. 2023, 145, 4828–4852.
- 15L. Dai, W. Liu, Y. Zhou, Z. Zeng, X. Hu, W. Cao, X. Feng, Angew. Chem. Int. Ed. 2021, 60, 26599–26603.
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