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D. Rodríguez-Lojo et al.
Letter
Synlett
References and Notes
additional portion of o-(trimethylsilyl)aryl triflate.
9,14-Diphenyl-12-(trimethylsilyl)benzo[f]tetraphen-11-yl
Trifluoromethanesulfonate (3)
(1) General reviews on aryne chemistry: (a) Hoffmann, R. W. Dehy-
drobenzene and Cycloalkynes; Academic Press: New York, 1967.
(b) Hart, H. The Chemistry of Triple-Bonded Functional Groups, In
Arynes and Heteroarynes; Patai, S.; Rappoport, Z., Eds.; Wiley:
Chichester, 1994, Suppl. C2 1017. (c) Pellisier, H.; Santelli, M.
Tetrahedron 2003, 59, 701. (d) Sanz, R. Org. Prep. Proced. Int.
2008, 40, 215.
(2) Kitamura, T. Aust. J. Chem. 2010, 98, 987.
(3) Himeshima, Y.; Sonoda, T.; Kobayashi, H. Chem. Lett. 1983,
1211.
(4) Representative metal-catalyzed transformations involving
arynes: (a) Peña, D.; Escudero, S.; Pérez, D.; Guitián, E.; Castedo,
L. Angew. Chem. Int. Ed. 1998, 37, 2659. (b) Peña, D.; Pérez, D.;
Guitián, E.; Castedo, L. J. Am. Chem. Soc. 1999, 121, 5827.
(c) Yokinawa, E.; Yamamoto, Y. Angew. Chem. Int. Ed. 2000, 39,
173. (d) Peña, D.; Pérez, D.; Guitián, E. Palladium-Catalyzed Cyc-
loaddition Reactions of Arynes, In Palladium in Organic Synthesis;
Vol. 14; Tsuji, J., Ed.; Springer: Weinheim, 2005, 109. (e) Liu, Z.;
Larock, R. C. J. Org. Chem. 2007, 72, 223. (f) Yoshida, H.; Ohshita,
J.; Kunai, A. Bull. Chem. Soc. Jpn. 2010, 83, 199. (g) Worlikar, S. A.;
Larock, R. C. Current. Org. React. 2011, 15, 3214.
(5) Representative novel metal-free transformations: (a) Peña, D.;
Pérez, D.; Guitián, E. Angew. Chem. Int. Ed. 2006, 45, 3579.
(b) Bhunia, A.; Yetra, S. R.; Biju, A. T. Chem. Soc. Rev. 2012, 41,
3140. (c) Bhunia, A.; Biju, A. T. Synlett 2014, 25, 608. (d) Criado,
A.; Vilas-Varela, M.; Cobas, A.; Pérez, D.; Peña, D.; Guitián, E. J.
Org. Chem. 2013, 78, 12637. (e) Dubrovskiy, A. V.; Markina, N.
A.; Larock, R. C. Org. Biomol. Chem. 2013, 11, 191.
Reaction of 1,3-diphenyl-2H-cyclopenta[l]phenanthren-2-one
(4, 243 mg, 0.637 mmol), 2,5-bis(trimethylsilyl)-1,4-phenylene
bis(trifluoromethanesulfonate) (1, 300 mg, 0.579 mmol), and
CsF (105 mg, 0.695 mmol) in MeCN–CH2Cl2 (2:1; 9 mL) afforded
3 (218 mg, 58%) as a greenish solid; mp 219–221 °C. 1H NMR
(250 MHZ, CDCl3): δ = 8.29 (d, J = 7.3 Hz, 2 H), 8.13 (s, 1 H), 7.85
(s, 1 H), 7.59 (d, J = 8.5 Hz, 2 H), 7.54 (m, 5 H), 7.54 (m, 5 H),
7.41–7.36 (m, 2 H), 7.04–6.98 (m, 2 H), 0.33 (s, 9 H) ppm. 13C
NMR (63 MHz, CDCl3): δ = 152.6 (C), 140.9 (C), 140.5 (C), 136.8
(CH), 135.4 (C), 135.2 (C), 132.7 (C), 132.3 (2 CH), 132.2 (C),
132.1 (2 CH), 132.1 (C), 131.9 (C), 130.8 (C), 130.6 (C), 130.55
(C), 130.50 (CH), 130.4 (CH), 129.8 (C), 129.3 (C), 129.1 (2 CH),
129.0 (2 CH), 128.0 (CH), 127.9 (CH), 127.3 (CH), 127.2 (CH),
125.9 (2 CH), 123.3 (2 CH), 115.7 (CH), –0.8 (3 CH3) ppm. MS
(EI): m/z (%) = 650 (30). HRMS (EI): m/z calcd for C38H29F3O3SSi:
650.1559; found: 650.1563.
5,6,7,8-Tetraphenyl-3-(trimethylsilyl)naphthalen-2-yl Triflu-
oromethanesulfonate (12)
Reaction of 2,3,4,5-tetraphenylcyclopenta-2,4-dien-1-one (10,
329 mg, 0.858 mmol), 2,5-bis(trimethylsilyl)-1,4-phenylene
bis(trifluoromethanesulfonate) (1, 404 mg, 0.780 mmol), and
CsF (142 mg, 0.936 mmol) in MeCN–CH2Cl2 (2:1; 11 mL)
afforded 12 (305 mg, 60%) as a white solid; mp 249–251 °C. 1H
NMR (300 MHZ, CDCl3): δ = 7.89 (s, 1 H), 7.59 (s, 1 H), 7.32–7.20
(m, 10 H), 6.92–6.87 (m, 10 H), 0.30 (s, 9 H) ppm. 13C NMR (75
MHz, CDCl3): δ = 152.8 (C), 140.7 (C), 139.9 (4C), 138.7 (2 C),
138.5 (C), 138.3 (C), 136.9 (CH), 133.4 (C), 131.1 (3 CH), 131.1 (4
CH), 130.9 (2 CH), 130.5 (C), 127.7 (2 CH), 127.6 (2 CH), 126.9
(CH), 126.7 (4 CH), 125.7 (CH), 125.6 (CH), 118.4 (q, J = 320 Hz,
CF3), 116.3 (CH), –0.9 (3 CH3) ppm. MS (EI): m/z (%) = 652.3 (70)
[M+], 504.3 (14), 293.3 (41), 147.1 (43). HRMS (EI): m/z calcd for
(6) (a) Tadross, P. M.; Stoltz, B. M. Chem. Rev. 2012, 112, 3550.
(b) Gampe, C. M.; Carreira, E. M. Angew. Chem. Int. Ed. 2012, 51,
3766.
(7) (a) Pérez, D.; Peña, D.; Guitián, E. Eur. J. Org. Chem. 2013, 5981.
(b) Li, J.; Zhang, Q. Synlett 2013, 24, 686.
C
38H31F3O3SSi: 652.1715; found: 652.1713.
(8) Peña, D.; Cobas, A.; Pérez, D.; Guitián, E.; Castedo, L. Synthesis
2002, 1454.
(9) Romero, C.; Peña, D.; Pérez, D.; Guitián, E. Chem. Eur. J. 2006, 12,
5677.
(10) Iglesias, B.; Cobas, A.; Pérez, D.; Guitián, E.; Vollhardt, K. P. C.
Org. Lett. 2004, 6, 3557.
(11) Sygula, A.; Sygula, R.; Kobryn, L. Org. Lett. 2008, 10, 3927.
(12) Duong, H. M.; Bendikov, M.; Steiger, D.; Zhang, Q.; Sonmez, G.;
Yamada, J.; Wudl, F. Org. Lett. 2003, 5, 4433.
(13) Kitamura, C.; Abe, Y.; Ohara, T.; Yoneda, A.; Kawase, T.;
Kobayashi, T.; Naito, H.; Komatsu, T. Chem. Eur. J. 2010, 16, 890.
(14) Alonso, J. M.; Díaz-Álvarez, A. E.; Criado, A.; Peña, D.; Pérez, D.;
Guitián, E. Angew. Chem. Int. Ed. 2012, 51, 173.
(15) Wooi, G. Y.; White, J. M. Org. Biomol. Chem. 2005, 3, 972.
(16) General Procedure
9,14-Diphenyl-12-(trimethylsilyl)dibenzo[de,qr]tetracen-11-
yl Trifluoromethanesulfonate (13)
Reaction of 9,11-diphenyl-10H-cyclopenta[e]pyren-10-one (11,
100 mg, 0.246 mmol), 2,5-bis(trimethylsilyl)-1,4-phenylene
bis(trifluoromethanesulfonate) (1, 116 mg, 0.224 mmol), and
CsF (41 mg, 0.269 mmol) in MeCN–CH2Cl2 (2:1; 9 mL) afforded
13 (66 mg, 40%) as a yellow solid; mp 279–281 °C. 1H NMR (500
MHZ, CDCl3): δ = 8.11 (s, 1 H), 7.90–7.85 (m, 6 H), 7.82 (s, 1 H),
7.56–7.48 (m, 10 H), 7.35 (td, J = 7.9, 2.2 Hz, 2 H), 0.32 (s, 9 H)
ppm. 13C NMR (126 MHz, CDCl3): δ = 153.0 (C), 141.7 (C), 141.4
(C), 137.3 (CH), 136.9 (C), 136.6 (C), 133.2 (C), 132.4 (2 CH),
132.2 (2 CH), 131.0 (C), 131.0 (C), 130.99 (C) 130.97 (C), 130.3
(C), 130.2 (C), 130.1 (C), 129.9 (C), 129.5 (2 CH), 129.4 (2 CH),
129.1 (CH), 129.0 (CH), 128.2 (CH), 128.1 (CH), 127.1 (CH),
127.1 (CH), 126.6 (CH), 126.4 (CH), 126.2 (C), 126.1 (C), 125.1
(CH), 125.0 (CH), 118.5 (q, J = 325 Hz, CF3), 116.1 (CH), –0.6 (3
CH3) ppm. MS (EI): m/z (%) = 674 (100) [M+], 541 (53), 448 (16).
5,6,7,8-Tetraphenyl-3-(trimethylsilyl)anthracen-2-yl Trifluo-
romethanesulfonate (17)
Reaction of 2,3,4,5-tetraphenylcyclopenta-2,4-dien-1-one (10,
126 mg, 0.329 mmol), 3,6-bis(trimethylsilyl)-naphthalene-2,7-
diyl bis(trifluoromethanesulfonate) (2, 115 mg, 0.299 mmol),
and CsF (55 mg, 0.359 mmol) in MeCN–CH2Cl2 (2:1; 9 mL)
afforded 17 (84 mg, 40%) as a white solid; mp 223–225 °C. 1H
NMR (300 MHZ, CDCl3): δ = 8.27 (s, 1 H), 8.22 (s, 1 H), 8.04 (s, 1
H), 7.82 (s, 1 H), 7.39–7.21 (m, 10 H), 7.01–6.78 (m, 10 H), 0.43
(s, 9 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 152.4 (C), 140.5 (2
C), 139.91 (C), 139.59 (C), 139.52 (C), 139.4 (C), 139.0 (CH),
To a solution of bisaryne precursor 1 or 2 and cyclopentadien-
one 4, 10, or 11 (110 mol%), in 2:1 MeCN–CH2Cl2, finely pow-
dered anhydrous CsF (120 mol%) was added, and the mixture
was stirred at 50 °C under argon atmosphere for 12 h. The
solvent was evaporated under reduced pressure, and the result-
ing mixture was purified by column chromatography (SiO2,
hexanes–CH2Cl2) to isolate the corresponding o-(trimethylsi-
lyl)aryl triflate. In some experiments, the intermediate Diels–
Alder adduct (e.g., 9) was detected in other fractions eluted
from the column, which were collected, concentrated under
vacuum, dissolved in tetrachloroethane, and refluxed for 12 h.
Evaporation of the solvent under vacuum and column chroma-
tography (SiO2, hexanes–CH2Cl2) of the residue afforded an
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 1633–1637