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Y. Tanji et al.
Letter
tonation pathway assisted by the pivalate ligand, affording
the palladacycle intermediate C. Finally, reductive elimina-
tion from D leads to the fluorene 3 with regeneration of the
Pd(0) species.
Simon, Y. C.; Coughlin, E. B.; Carter, K. R. Chem. Commun. 2009,
4950. (i) Shabashov, D.; Maldonado, J. R. M.; Daugulis, O. J. Org.
Chem. 2008, 73, 7818. (j) Alessi, M.; Larkin, A. L.; Ogilvie, K. A.;
Green, L. A.; Lai, S.; Lopez, S.; Snieckus, V. J. Org. Chem. 2007, 72,
1588. (k) Barluenga, J.; Trincado, M.; Rubio, E.; González, J. M.
In conclusion, a practical method was developed for the
synthesis of fluorenes through Pd-catalyzed intramolecular
cyclization of 2-arylbenzyl chlorides. Under these reaction
conditions, pivalic acid acts as an efficient source of carbox-
ylate ligand for the Pd catalyst. A variety of fluorene deriva-
tives were readily obtained in excellent yields at room tem-
perature.
Angew. Chem. Int. Ed. 2006, 45, 3140. (l) Tilly, D.; Samanta, S. S.;
Castanet, A.-S.; De, A.; Mortier, J. Eur. J. Org. Chem. 2006, 174.
(m) Wong, K.-T.; Chi, L.-C.; Huang, S.-C.; Liao, Y.-L.; Liu, Y.-L.;
Wang, Y. Org. Lett. 2006, 8, 5029. (n) Wong, K.-T.; Hwu, T.-Y.;
Balaiah, A.; Chao, T.-C.; Fang, F.-C.; Lee, C.-T.; Peng, Y.-C. Org.
Lett. 2006, 8, 1415.
(
5) For reviews, see: (a) Kaiser, R. P.; Caivano, I.; Kotora, M. Tetrahe-
dron 2019, 75, 2981. (b) Zhou, A.-H.; Pan, F.; Zhu, C.; Ye, L.-W.
Chem. Eur. J. 2015, 21, 10278.
(
6) Selected examples, see: (a) Nishida, M.; Shintani, R. Chem. Eur. J.
Funding Information
2019, 25, 7475. (b) Ma, D.; Shi, G.; Wu, Z.; Ji, X.; Zhang, Y. J. Org.
Chem. 2018, 83, 1065. (c) Corrie, T. J. A.; Ball, L. T.; Russell, C. A.;
Lloyd-Jones, G. C. J. Am. Chem. Soc. 2017, 139, 245. (d) Song, J.;
Sun, W.; Li, Y.; Wei, F.; Liu, C.; Qian, Y.; Chen, S. Chem. Asian J.
This work was supported by JSPS KAKENHI Grant Number 18H04257:
Precisely Designed Catalysts with Customized Scaffolding (T. Fujiha-
ra), and Grant Number 17H03096 in Grant-in-Aid for Scientific Re-
search B (Y. Tsuji) from MEXT, Japan. Y. Tanji is grateful for a research
2016, 11, 211. (e) Shi, G.; Chen, D.; Jiang, H.; Zhang, Y.; Zhang, Y.
Org. Lett. 2016, 18, 2958. (f) Hirano, M.; Kawazu, S.; Komine, N.
Organometallics 2014, 33, 1921. (g) Liu, T.-P.; Xing, C.-H.; Hu, Q.-
S. Angew. Chem. Int. Ed. 2010, 49, 2909. (h) Tobisu, M.; Kita, Y.;
Ano, Y.; Chatani, N. J. Am. Chem. Soc. 2008, 130, 15982.
fellowship from JSPS for Young Scientists.
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Supporting Information
(i) Shimizu, M.; Mochida, K.; Hiyama, T. Angew. Chem. Int. Ed.
Supporting information for this article is available online at
2008, 47, 9760. (j) Dong, C.-G.; Hu, Q.-S. Angew. Chem. Int. Ed.
2006, 45, 2289. (k) Fuchibe, K.; Akiyama, T. J. Am. Chem. Soc.
https://doi.org/10.1055/s-0039-1690812.
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2006, 128, 1434.
(7) Hsiao, C.-C.; Lin, Y.-K.; Liu, C.-J.; Wu, T.-C.; Wu, Y.-T. Adv. Synth.
Catal. 2010, 352, 3267.
References and Notes
(
(
8) Hwang, S. J.; Kim, H. J.; Chang, S. Org. Lett. 2009, 11, 4588.
9) Tanji, Y.; Mitsutake, N.; Fujihara, T.; Tsuji, Y. Angew. Chem. Int.
Ed. 2018, 57, 10314.
(1) (a) Dennler, G.; Scharber, M. C.; Brabec, C. J. Adv. Mater. (Wein-
heim, Ger.) 2009, 21, 1323. (b) Inganäs, O.; Zhang, F.; Andersson,
M. R. Acc. Chem. Res. 2009, 42, 1731. (c) Anthony, J. E. Chem. Rev.
(
10) Fujihara, T.; Yoshida, A.; Satou, M.; Tanji, Y.; Terao, J.; Tsuji, Y.
Catal. Commun. 2016, 84, 71.
11) 9H-Fluorene (3a); Typical Procedure
2
2
006, 106, 5028. (d) Hughes, G.; Bryce, M. R. J. Mater. Chem.
005, 15, 94. (e) Scherf, U.; List, E. J. W. Adv. Mater. (Weinheim,
(
Ger.) 2002, 14, 477. (f) Bernius, M. T.; Inbasekaran, M.; O’Brien,
J.; Wu, W. Adv. Mater. (Weinheim, Ger.) 2000, 12, 1737.
In advance, Cs CO was dried by heating under vacuum for 3 h
2
3
then stored in a glovebox. A 10-mL Schlenk flask was charged
with the dried Cs CO (0.16 g, 0.50 mmol) in a glovebox, then
(
2) (a) Xie, L.-H.; Yin, C.-R.; Lai, W.-Y.; Fan, Q.-L.; Huang, W. Prog.
Polym. Sci. 2012, 37, 1192. (b) Miyatake, K.; Bae, B.; Watanabe,
M. Polym. Chem. 2011, 2, 1919. (c) Koyama, Y.; Nakazono, K.;
Hayashi, H.; Tataka, T. Chem. Lett. 2010, 39, 2. (d) Wong, K.-T.;
Chien, Y.-Y.; Chen, R.-T.; Wang, C.-F.; Lin, Y.-T.; Chiang, H.-H.;
Hsieh, P.-Y.; Wu, C.-C.; Chou, C.-H.; Su, Y.-O.; Lee, G.-H.; Peng, S.-
M. J. Am. Chem. Soc. 2002, 124, 11576.
2
3
taken out of glovebox and dried by heating under a vacuum for
at least 5 min. The flask was backfilled with argon and then
PdCl (PPh ) (1.4 mg, 0.0020 mmol, 1.0 mol%) and pivalic acid
2
3 2
(
1c; 20 mg, 0.20 mmol, 1.0 equiv) were added. The flask was
then evacuated and backfilled with argon three times. THF
0.50 mL) and 2a (37 L, 0.20 mmol) were added, and the
(
(
3) (a) Shi, Y.; Gao, S. Tetrahedron 2016, 72, 1717. (b) Ribeiro, C.;
Brogueira, P.; Lavareda, G.; Carvalho, C. N.; Amaral, A.; Santos,
L.; Morgado, J.; Scherf, U.; Bonifácio, V. D. Biosens. Bioelectron.
mixture was stirred at 25 °C for 18 h. The mixture was then
analyzed by GC with tetradecane (50 L) as an internal stan-
dard. H O (5 mL) and EtOAc (5 mL) were added, and the mixture
2
2010, 26, 1662. (c) Morgan, L. R.; Thangaraj, K.; LeBlanc, B.;
was extracted with EtOAc (3 × 5 mL). The collected organic
layers were combined, washed with brine (5 mL), dried
Rodgers, A.; Wolford, L. T.; Hooper, C. L.; Fan, D.; Jursic, B. S.
J. Med. Chem. 2003, 46, 4552.
(
MgSO ), and concentrated. The residue was purified by chro-
4
(
4) (a) Shi, Z.; Glorius, F. Chem. Sci. 2013, 4, 829. (b) Wertz, S.;
Leifert, D.; Studer, A. Org. Lett. 2013, 15, 928. (c) Seo, S.; Slater,
M.; Greaney, M. F. Org. Lett. 2012, 14, 2650. (d) Chinnagolla, R.
K.; Jeganmohan, M. Org. Lett. 2012, 14, 5246. (e) Wang, S.-G.;
Han, L.; Zeng, M.; Sun, F.-L.; Zhang, W.; You, S.-L. Org. Biomol.
Chem. 2012, 10, 3202. (f) Lockner, J. W.; Dixon, D. D.; Risgaard,
R.; Baran, P. S. Org. Lett. 2011, 13, 5628. (g) Sun, F.-L.; Zeng, M.;
Gu, Q.; You, S.-L. Chem. Eur. J. 2009, 15, 8709. (h) Peterson, J. J.;
matography (silica gel, hexane–acetone) to give a colorless
solid; yield: 32.1 mg (96%).
1
H NMR (400 MHz, CDCl ): = 7.80 (d, J = 7.8 Hz, 2 H), 7.56 (d,
3
J = 7.3 Hz, 2 H), 7.39 (t, J = 7.3 Hz, 2 H), 7.31 (td, J = 7.4, 1.1 Hz, 2
13
H), 3.92 (s, 2 H). C NMR (100 MHz, CDCl ): = 143.2, 141.7,
1
3
+
26.7, 126.7, 125.0, 119.8, 36.9. EI-HRMS: m/z: [M – H] calcd
for C13H : 165.0704; found: 165.0702.
9
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2020. Thieme. All rights reserved. Synlett 2020, 31, 805–808