Advanced Synthesis & Catalysis
10.1002/adsc.201900283
iminyl radical intermediate I, which undergoes a 1,5-
hydrogen transfer process to form the carbon centered
radical intermediate II. Subsequently, intermediate II
undergoes intramolecular homolytic aromatic
[1] a) Y. Qin, L. H. Zhu and S. Z. Luo, Chem. Rev., 2017,
117, 9433−9520; b) C. M. Che, V. K. Y. Lo, C. Y.
Zhou and J. S. Huang, Chem. Soc. Rev., 2011, 40,
1950-1975; c) C. L. Sun, B. J. Li and Z. J. Shi, Chem.
Rev., 2011, 111, 1293-1314; d) G. He, B. Wang, W. A.
Nack and G. Chen, Acc. Chem. Res., 2016, 49, 635-645.
[13]
substitution (HAS) in a Minisci-type reaction
to
generate intermediate III. The iron(n) catalyst can be
regenerated by oxidizing intermediate III,
subsequently intermediate IV can be formed after
deprotonation. Finally, intermediate IV undergoes a
hydrolysis process to give the desired ketone product
[
[
[
2] a) A. Dhakshinamoorthy, A. M. Asiri and H Garcia,
ACS Catal., 2019, 9, 1081-1102; b) T. Gensch, M. N.
Hopkinson, F. Glorius and J. Wencel-Delord, Chem.
Soc. Rev., 2016, 45, 2900-2936; c) R. Giri, B. F. Shi, K.
M. Engle, N. Maugel and J. Q. Yu, Chem. Soc. Rev.,
2a.
2
009, 38, 3242-3272.
3] a) J. Wencel-Delord, T. Droege, F. Liu and F. Glorius,
Chem. Soc. Rev., 2011, 40, 4740-4761; b) K. M. Engle,
T. S Mei, M. Wasa, and J. Q. Yu, Acc. Chem. Res.,
2
2
012, 45, 788-802; c) J. F. Hartwig, Chem. Soc. Rev.,
011, 40, 1992-2002; d) R. Vanjari and K. N. Singh,
Chem. Soc. Rev., 2015, 44, 8062-8096.
4]a) J. He, M. Wasa, K. S. L. Chan, Q. Shao and J. Q. Yu,
Chem. Rev., 2017, 117, 8754-8786; b) P. Herrmann and
T. Bach, Chem. Soc. Rev., 2011, 40, 2022-2038; c) Z.
Huang, H. N. Lim, F. Mo, M. C. Young and G. Dong,
Chem. Soc. Rev., 2015, 44, 7764-7786; d) T. A.
Ramirez, B. Zhao and Y. Shi, Chem. Soc. Rev., 2012,
4
1, 931-942; e) F. Kakiuchi and S. Murai, Acc. Chem.
Res., 2002, 35, 826-834; f) S. Gaillard, C. S. J. Cazin
and S. P. Nolan, Acc. Chem. Res., 2012, 45, 778-787.
Scheme 3. Proposed reaction mechanism.
[
5] For selected reviews, see: a) X. Q. Hu, J. R. Chen and
W. J. Xiao, Angew. Chem., Int. Ed. 2017, 56, 1960-
1962; b) M. Nechab, S. Mondal and M. P. Bertrand,
Chem. Eur. J., 2014, 20, 16034-16059; c) M. Salamone
and M. Bietti, Acc. Chem. Res., 2015, 48, 2895-2903;
d) W. Li, W. Xu, J. Xie, S. Yu and C. Zhu, Chem. Soc.
Rev., 2018, 47, 654-667; For representative examples,
see: e) Z. Liu, H. Xiao, B. Zhang, H. Shen, L. Zhu and
C. Li, Angew. Chem., Int. Ed. 2019, 58, 2510-2513; f)
D. P. Curran, D. Kim, H. T. Liu and W. Shen, J. Am.
Chem. Soc., 1988, 110, 5900-5902; g) H. Chen, L. Guo
and S. Yu, Org. Lett., 2018, 20, 6255-6259; h) D. F.
Chen, J. C. K. Chu and T. Rovis, J. Am. Chem. Soc.,
2017, 139, 14897-14900; i) A. Hu, J.-J. Guo, H. Pan, H.
Tang, Z. Gao and Z. Zuo, J. Am. Chem. Soc., 2018, 140,
In conclusion, we have developed an iron-
catalyzed intramolecular arylation of oxime esters for
the synthesis of dihydronaphthalenones. In the
presence of Fe(acac) as the catalyst under air, the
3
desired ketone products were obtained in moderate to
[14]
good yields with complete chemoselectivities.
Experimental Section
In a 25 mL sealed tube with a magnetic stirring bar was
added with 1a (0.4 mmol, 118.2 mg), Fe(acac) (0.04
mmol, 14 mg), H O (10 equiv., 72 uL) and MeCN (4 mL)
under an open atmosphere, the mixture was stirred at
20 °C for 12 h. Then the mixture was cooled to room
temperature, and the reaction was quenched with sat. aq.
3
2
1
612-1616.
1
[6] a) X. Wu, H. Zhang, N. Tang, Z. Wu, D. Wang, M. Ji,
Y. Xu, M. Wang and C. Zhu, Nat, Commun., 2018, 9,
3
and C. Zhu, Angew. Chem., Int. Ed. 2018, 57, 1640-
1644; c) G.-X. Li, X. Hu, G. He and G. Chen, Chem.
Sci., 2019, 10, 688-693; d) W. Shu, A. Lorente, E.
Gómez-Bengoa and C. Nevado, Nat, Commun., 2017, 8,
3
NaHCO , extracted with EtOAc (3 x 5 mL). The organic
343; b) X. Wu, M. Wang, L. Huan, D. Wang, J. Wang
solvent was then evaporated under reduced pressure. The
crude product was purified by column chromatography on
silica gel (pentane/ethyl acetate = 20:10 to 10:1) to give
pure product 3a as colorless oil in 70% yield (48.8 mg).
1
3832; e) R. Wang, Y. Li, R.-X. Jin and X.-S. Wang,
Acknowledgements
Chem. Sci., 2017, 8, 3838-3842; f) R. Wang, R. X. Jin,
Z. Y. Qin, K. J. Bian and X. S. Wang, Chem. Commun.,
2017, 53, 12229-12232.
The authors thank the Chinese Scholarship Council for financial
support. The analytical support from Dr W. Baumann, Dr C.
Fischer, S. Buchholz, and S. Schareina is gratefully
acknowledged. We also appreciate the general support from
Professor Armin Bꢀrner and Professor Matthias Beller in LIKAT.
[
7]a) A. R. Forrester, M. Gill and R. H. Thomson, J. Chem.
Soc., Chem. Commun., 1976, 677-678; b) J. J. Zhang, X.
H. Duan, Y. Wu, J. C. Yang and L. N. Guo, Chem. Sci.,
2
019, 10, 161-166; c) X. Shen, J. J. Zhao and S. Yu,
Org. Lett., 2018, 20, 5523-5527; d) E. M. Dauncey, S.
P. Morcillo, J. J. Douglas, N. S. Sheikh and D. Leonori,
References
4
This article is protected by copyright. All rights reserved.