10.1002/anie.202001211
Angewandte Chemie International Edition
COMMUNICATION
PdCl2 (5.0 mol%)
PCy3·HBF4 (10 mol%)
K2CO3 (3.0 equiv)
tBuCO2H (0.50 equiv)
FeCl3
OTf
CH2Cl2, 0 ºC, 2.5 h
CPME
140 ºC, 20 h
1j
2j
46%
6j
86%
2j' (regioisomer)
Trace
tBu
tBu
tBu
tBu
tBu
PdCl2 (5.0 mol%)
PCy3·HBF4 (10 mol%)
K2CO3 (3.0 equiv)
tBuCO2H (0.50 equiv)
FeCl3
OTf
CPME
140 ºC, 20 h
CH2Cl2, 0 ºC, 2.5 h
tBu
tBu
tBu
tBu
tBu
1k
2k
69%
6k
92%
Proposal for a new retrosynthesis of polybenzoacenes by annulative dimerization
R
R
R
R
R
Ar
Ar
Ar
Ar
Ar
OTf
R
R
R
R
R
Figure 5. Regioselective annulative dimerization and its application for the synthesis of polybenzoacenes.
[2]
a) L. Chen, Y. Hernandez, X. Feng, K. Müllen, Angew. Chem., Int. Ed.
2012, 51, 7640–7654; b) Y. Segawa, H. Ito, K. Itami, Nat. Rev. Mater.
2016, 1, 15002.
In summary, we have developed an annulative dimerization
of phenylene triflate through a two-fold inter- and intramolecular
C–H activation. The resulting partially fused PAHs were
derivatized into a variety of fully fused PAHs. The two-step
sequence enables the rapid synthesis of polybenzoacenes
[3]
Reviews on C–H functionalization chemistry: a) F.-X. Felpin, S.
Sengupta, Chem. Soc. Rev. 2019, 48, 1150–1193; b) H. Wang, X. Gao,
Z. Lv, T. Abdelilah, A. Lei, Chem. Rev. 2019, 119, 6769–6787; c) P.
Gandeepan, T. Müller, D. Zell, G. Cera, S. Warratz, L. Ackermann,
Chem. Rev. 2019, 119, 2192–2452; d) J. Wang, G. Dong, Chem. Rev.
2019, 119, 7478–7528.
through
methodology
regioselective
proposes
annulative
new
dimerization.
retrosynthesis
This
of
a
polybenzoacenes with annulative dimerization as the key
reaction. Synthesis of larger PAHs via this strategy is ongoing in
our laboratory.
[4]
a) H. Ito, Y. Segawa, K. Murakami, K. Itami, J. Am. Chem. Soc. 2019,
141, 3–10; b) Y. Segawa, T. Maekawa, K. Itami, Angew. Chem., Int. Ed.
2014, 53, 66–81; c) H. Ito, K. Ozaki, K. Itami, Angew. Chem., Int. Ed.
2017, 56, 11144–11164.
[5]
[6]
Y. Koga, T. Kaneda, Y. Saito, K. Murakami, K. Itami, Science 2018, 359,
435–439.
Acknowledgements
a) E. Wenkert, E. L. Michelotti, C. S. Swindell, J. Am. Chem. Soc. 1979,
101, 2246–2247; b) A. R. Ehle, Q. Zhou, M. P. Watson, Org. Lett. 2012,
14, 1202–1205; c) A. Correa, T. León, R. Martin, J. Am. Chem. Soc.
2014, 136, 1062–1069; d) M. Tobisu, A. Yasutome, H. Kinuta, K.
Nakamura, N. Chatani, Org. Lett. 2014, 16, 5572–5575; e) K. Muto, J.
Yamaguchi, K. Itami, J. Am. Chem. Soc. 2012, 134, 169–172.
a) Fujimoto, H.; Yahiro, M.; Yukiwaki, S.; Kusuhara, K.; Nakamura, N.;
Suekane, T.; Wei, H.; Imanishi, K.; Inada, K.; Adachi, C. Appl. Phys.
Lett. 2016, 109, 243302; b) H. Becker, I. Bach, M. Holbach, J.
Schwaiger, H. Spretizer, SID Int. Symp. Digest Tech. Papers 2010, 41,
39–42; c) A. Feissner, K. Stegmaier, C. Melzer, H. von Seggern, T.
Schwalm, M. Rehahn, Chem. Mater. 2009, 21, 4288–4298.
C. Zhu, D. Wang, D. Wang, Y. Zhao, W.-Y. Sun, Z. Shi, Angew. Chem.,
Int. Ed. 2018, 57, 8848–8853.
This work was supported by JST ERATO Grant Numbers
JPMJER1302 (K.I.), Japan, JSPS KAKENHI (JP19H05463 to
K.I., JP17H04868 and JP19H02700 to K.M.), the Noguchi
Institute (K.M.), and Shorai Foundation for Science and
Technology (K.M.). We are grateful to Dr. Yasutomo Segawa for
assistance with X-ray crystal structure analysis and fruitful
discussions. Dr. Greco González Miera and Ms. Yip Shu Jan are
acknowledged for proofread. ITbM is supported by the World
Premier International Research Center Initiative (WPI), Japan.
[7]
[8]
[9]
Keywords: palladium • annulative dimerization • phenylene
a) A. G. Sergeev, J. F. Hartwig, Science 2011, 332, 439–443; b) H.
Saito, K. Otsuka, K. Nogi, H. Yorimitsu, J. Am. Chem. Soc. 2016, 138,
15315–15318.
triflate • polybenzoacene • C–H activation
[1]
a) S. Allard, M. Forster, B. Souharce, H. Thiem, U. Scherf, Angew.
Chem., Int. Ed. 2008, 47, 4070–4098; b) A. Facchetti, Chem. Mater.
2011, 23, 733–758; c) C. Wang, H. Dong, W. Hu, Y. Liu, D. Zhu, Chem.
Rev. 2012, 112, 2208–2267; d) M. D. Watson, A. Fechtenkötter, K.
Müllen, Chem. Rev. 2001, 101, 1267–1300.
[10] a) M. Grzybowski, K. Skonieczny, H. Butenschön, D. T. Gryko, Angew.
Chem., Int. Ed. 2013, 52, 9900–9930; b) M. Grzybowski, B. Sadowski,
H. Butenschön, D. T. Gryko, Angew. Chem. Int. Ed. 2020, 59, 2998–
3027.
[11] Our previous syntheses from pyrene as the starting material: a) K.
Mochida, K. Kawasumi, Y. Segawa, K. Itami, J. Am. Chem. Soc. 2011,
133, 10716–10719; b) K. Ozaki, K. Kawasumi, M. Shibata, K. Itami,
4
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