10.1002/adsc.202001080
Advanced Synthesis & Catalysis
This work was supported by National Natural Science Foundation
of China (81672952), Guangzhou Science and Technology
Program (201807010041), Guangdong Provincial Department of
Education
Youth
Innovation
Talents
Project
(No.
2017GkQNCX099), China; Guangdong Medical Research Fund
Project (No. A2018497), China.
References
[1]
K. Padget, A. Stewart, P. Charlton, M. J. Tilby, C.
A. Austin, Biochem. Pharmacol. 2000, 60, 817-
821.
[2]
a) H. S. Hong, I. Maezawa, M. Budamagunta, S.
Rana, A. Shi, R. Vassar, R. Liu, K. S. Lam, R. H.
Cheng, D. H. Hua, J. C. Voss, L. W. Jin,
Neurobiol. Aging. 2010, 31, 1690-1699; b)
Suman, A. Bagui, A. Garg, B. Tyagi, V. Gupta, S.
P. Singh, Chem. Commun. 2018, 54, 4001-4004.
M. Yoshida, Y. Kabe, T. Wada, A. Asai, H.
Handa, Mol. Pharmacol. 2008, 73, 987-994.
a) N. A. Romero, D. A. Nicewicz, J. Am. Chem.
Soc. 2014, 136, 17024-17035; b) N. A. Romero,
D. A. Nicewicz, Chem. Rev. 2016, 116, 10075-
10166; c) C. Hamada, Y. Usuki, D. Takeuchi, H.
Ogawa, R. Abe, T. Satoh, Org. Lett. 2019, 21,
965-968. d) D. S. Hamilton, D. A. Nicewicz, J.
Am. Chem. Soc. 2012, 134, 18577-18580; e) A.
Joshi-Pangu, F. Levesque, H. G. Roth, S. F.
Oliver, L. C. Campeau, D. Nicewicz, D. A.
DiRocco, J. Org. Chem. 2016, 81, 7244-7249; f)
M. Majek, A. Jacobi von Wangelin, Acc. Chem.
Res. 2016, 49, 2316-2327; g) T. M. Nguyen, N.
Manohar, D. A. Nicewicz, Angew. Chem. Int. Ed.
2014, 53, 6198-6201.
[3]
[4]
Scheme 6. Proposed mechanism.
elimination to form unwanted E-1 which was
evidenced by the formation of 6a (Scheme 5b). In the
presence of formate, the direction of reductive Heck
reaction was accelerated to provide the expected
fluorene 4.
In summary, we have successfully developed a
concise method to construct structurally diverse
fluorene derivatives from cyclic diaryliodoniums. The
reactions involved one conventional Mizoroki-Heck
reaction and one reductive Heck-reaction between
cyclic diaryliodoniums and terminal alkenes. Except
traditional acrylates and alkenes with -electron
withdrawing functional groups, both aryl and alkyl
alkenes were suitable. The current method is
straightforward for the synthesis of fluorenes,
providing a complementary strategy to the reported
synthetic routes.
[5]
[6]
Y. Chen, P. Lu, Y. Wang, Org. Lett. 2019, 21,
2130-2133.
Leonard N. Horowitz, Scott R. Spielman, Charles
R. Webb, Joel Morganroth, Allan M. Greenspan,
American. Heart. Journal. 1985, 110, 784-788.
M. Zhang, H. Luo, Z. Xi, R. Ekaterina, PloS. One.
2015, 10, e0126082/1-e0126082/13.
a) A. Goel, A. Kumar, A. Raghuvanshi, Chem.
Rev. 2013, 113, 1614-1640; b) T. W. Janina
Bucher, Svenja Taschinski, Eleni Sachs, David
Ascough, F. R. Matthias Rudolph, A. Stephen K.
Hashmi, Adv. Synth. Catal. 2017, 359, 225-233; c)
S. Kumar, C. Cruz-Hernandez, S. Pal, R. K.
Saunthwal, M. Patel, R. K. Tiwari, E. Juaristi, A.
K. Verma, J. Org. Chem. 2015, 80, 10548-10560;
d) S. Pal, D. Choudhary, M. Jainth, S. Kumar, R.
K. Tiwari, A. K. Verma, J. Org. Chem. 2016, 81,
9356-9371.
J. Barluenga, M. Trincado, E. Rubio, J. M.
Gonzalez, Angew. Chem. Int. Ed. 2006, 45, 3140-
3143.
a) D. S. B. Mohmed K. Anwer, J. Gordon Roney,
Arno F. Spatola, J. Org. Chem. 1989, 54, 1284-
1289; b) Y. Y. Ji, L. L. Lu, Y. C. Shi, L. X. Shao,
Org. Biomol. Chem. 2014, 12, 8488-8498.
a) K. Morimoto, M. Itoh, K. Hirano, T. Satoh, Y.
Shibata, K. Tanaka, M. Miura, Angew. Chem. Int.
Ed. 2012, 51, 5359-5362; b) L. Donnini, Riv. Crit.
[7]
[8]
Experimental Section
To a reaction tube, was added cyclic diaryliodonium
salt 2a (0.2 mmol), alkenes 3 (0.4 mmol), Pd(PPh3)4
(0.1 equiv), Et3N (0.6 mmol), HCOONa (0.4 mmol),
1,2-dichloroethane (3.0 mL). Then, the tube was
sealed, degassed and recharged with argon. The
o
reaction proceeded at 100 C for 15 h under argon
atmosphere. Finally, dichloromethane (20 mL) was
added to dilute the reaction mixture. The diluted
mixture was washed with H2O (2 mL x 3) and brine
(2 mL), dried over anhydrous Na2SO4, and
concentrated under reduced pressure. The residue was
purified by column chromatography on a silica gel
(petroleum/EtOAc = 50/1-20/1) to provide 4.
[9]
[10]
[11]
Acknowledgements
4
This article is protected by copyright. All rights reserved.