Organic Letters
Letter
Tucek, J.; Zboril, R. Chem. Rev. 2015, 115, 4744. (e) Sun, Z.; Ye, Q.;
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experiments were also conducted, and the intramolecular and
intermolecular KIE values of [D1]-1a and 1a/[D5]-1a were
found to be kH/kD = 1.6 and 3.8, respectively.8 These results
indicate that the first step is C−H arylation to give compound
A,6,12 and the C−H bond activation might be involved in the
rate-determining step. Furthermore, the newly generated TFA
during the C−H bond activation reaction is the catalyst of the
following A to 3 cascade cyclization (Scheme 5).
In summary, we have developed a straightforward and
efficient procedure for the preparation of phenanthrenes from
readily available starting materials via a sequence combining γ-
C(sp2)−H arylation, cationic cyclization, dehydration, and 1,2-
migration. A variety of symmetric and unsymmetric phenan-
threne derivatives with a high degree of functionalization
including triphenylenes were synthesized by this protocol. We
believe that this operationally simple protocol will be highly
attractive to other chemists in manipulating phenanthrenes for
materials science and organic synthesis. Further studies on
elucidating the mechanism and extending the application of
this protocol are underway.
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ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Experimental procedures, characterization data for all
new compounds, and copies of 1H and 13C NMR
Accession Codes
tallographic data for this paper. These data can be obtained
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
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AUTHOR INFORMATION
Corresponding Authors
■
ORCID
Notes
̌
Petuskova, J.; Thiel, W.; Alcarazo, M. J. Am. Chem. Soc. 2013, 135,
18815. (j) Kwon, Y.; Cho, H.; Kim, S. Org. Lett. 2013, 15, 920.
(k) Yamamoto, Y.; Matsui, K.; Shibuya, M. Chem. - Eur. J. 2015, 21,
7245. (l) Jin, R.; Chen, Y.; Liu, W.; Xu, D.; Li, Y.; Ding, A.; Guo, H.
Chem. Commun. 2016, 52, 9909. (m) Shimizu, M.; Nagao, I.;
Tomioka, Y.; Hiyama, T. Angew. Chem., Int. Ed. 2008, 47, 8096.
(n) McAtee, C. C.; Riehl, P. S.; Schindler, C. S. J. Am. Chem. Soc.
2017, 139, 2960. (o) Matsuoka, W.; Ito, H.; Itami, K. Angew. Chem.,
Int. Ed. 2017, 56, 12224.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the National Natural Science Foundation of China
(NSFC-21672170), the Natural Science Basic Research Plan in
Shaanxi Province of China (2018JC-020, 2018JM2029), and
the Key Science and Technology Innovation Team of Shaanxi
Province (2017KCT-37) for financial support.
́ ́
(5) (a) Pena, D.; Perez, D.; Guitian, E.; Castedo, L. J. Am. Chem. Soc.
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1999, 121, 5827. (b) Catellani, M.; Motti, E.; Baratta, S. Org. Lett.
2001, 3, 3611. (c) Bhuvaneswari, S.; Jeganmohan, M.; Cheng, C.-H.
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