E
H. Kurata et al.
Cluster
Synlett
tBu
tBu
tBu
O
tBu
O
O
O
tBu
tBu
tBu
tBu
tBu
tBu
tBu
e–
tBu
tBu
S
S
O
O
O
O
tBu
tBu
tBu
tBu
3–
3
tBu
O
O
tBu
tBu
O
O
tBu
tBu
tBu
tBu
tBu
tBu
e–
e–
tBu
tBu
S
O
O
S
O
O
tBu
tBu
O
tBu
tBu
32–
33–
tBu
tBu
O
tBu
tBu
tBu
e–
tBu
S
O
O
tBu
tBu
34–
Scheme 3 Redox process of 3
ester, 1988, Part 2, Vol. 2, 1419. (c) Zhou, J.; Rieker, A. J. Chem.
Soc., Perkin Trans. 2 1997, 931. (d) Zhou, J.; Felderhoff, M.;
Smelkovae, N.; Gornastaev, L. M.; Rieker, A. J. Chem. Soc., Perkin
Trans. 2 1998, 343.
Chem. Int. Ed. 2005, 44, 316. (e) Kurata, H.; Takehara, Y.;
Matsumoto, K.; Kawase, T.; Oda, M. Chem. Lett. 2005, 34, 1660.
(f) Kurata, H.; Takehara, Y.; Kim, S.; Sakai, K.; Matsumoto, K.;
Kawase, T.; Oda, M. Synlett 2007, 2053.
(2) (a) Takahashi, K.; Suzuki, T. J. Am. Chem. Soc. 1989, 111, 5483.
(b) Takahashi, K.; Suzuki, T.; Akiyama, K.; Ikegami, Y.; Fukazawa,
Y. J. Am. Chem. Soc. 1991, 113, 4576. (c) Takahashi, K.; Gunji, A.;
Yanagi, K.; Miki, M. J. Org. Chem. 1996, 61, 4784. (d) Takahashi,
K.; Fujita, S.; Akiyama, K.; Miki, M.; Yanagi, K. Angew. Chem. Int.
Ed. 1998, 37, 2484. (e) Lanata, M.; Bertarelli, C.; Gallazzi, M. C.;
Bianco, A.; Del Zoppo, M.; Zerbi, G. Synth. Met. 2003, 138, 357.
(f) D'Amore, F.; Lanata, M.; Pietralunga, S. M.; Gallazzi, M. C.;
Zerbi, G. Opt. Mater. 2004, 24, 661. (g) Di Motta, S.; Negri, F.;
Fazzi, D.; Castiglioni, C.; Canesi, E. V. J. Phys. Chem. Lett. 2010, 1,
3334. (h) Fazzi, D.; Canesi, E. V.; Negri, F.; Bertarelli, C.;
Castiglioni, C. ChemPhysChem 2010, 11, 3685. (i) Canesi, E. V.;
Fazzi, D.; Colella, L.; Bertarelli, C.; Castiglioni, C. J. Am. Chem. Soc.
2012, 134, 19070. (j) Colella, L.; Brambilla, L.; Nardone, V.;
Parisini, E.; Castiglioni, C.; Bertarelli, C. Phys. Chem. Chem. Phys.
2015, 17, 10426. (k) Kan, Z.; Colella, L.; Canesi, E. V.; Vorobiev,
A.; Skrypnychuk, V.; Terraneo, G.; Barbero, D. R.; Bertarelli, C.;
MacKenzie, R. C. I.; Keivanidis, P. E. J. Mater. Chem. A 2016, 4,
1195.
(4) Sugimoto, T.; Nagatomi, T.; Ando, H.; Yoshida, Z. Angew. Chem.,
Int. Ed. Engl. 1988, 27, 560.
(5) Experimental details of syntheses of 3–6 are provided in the
Supporting Information.
(6) Dang, T. T.; Rasool, N.; Reinkea, H.; Langer, P. Tetrahedron Lett.
2007, 48, 845.
(7) Tetrakis(4-hydroxy-3,5-di-tert-butylphenyl)thiophene (5)
Colorless crystals; mp 206–207 °C (decomp.). 1H NMR (400
MHz, CDCl3): δ = 7.09 (s, 4 H), 6.66 (s, 4 H), 5.08 (s, 2 H), 4.92 (s,
2 H), 1.28 (s, 36 H), 1.18 (s, 36 H). 13C NMR (75 MHz, CDCl3): δ =
152.76, 151.83, 139.99, 137.14, 135.40, 135.14, 128.51, 127.61,
126.18, 125.94, 34.20, 34.06, 30.36, 30.20. MS (MALDI): m/z =
901.0 [M+], 902.0 [M + 1]+. IR (KBr): ν = 3644 (s), 2957 (s), 2915
(m), 2872 (m), 1433 (s), 1391 (w), 1361 (m), 1313 (m), 1234 (s),
1205 (w), 1156 (s), 1120 (m), 887 (m), 768 (m) cm−1. UV-vis
(CH2Cl2): λmax (log ε) = 332 (4.17), 284 (4.30), 246 (4.43), 228
(4.55) nm. Anal. Calcd for C60H84O4S: C, 79.95; H, 9.39. Found: C,
79.75; H, 9.57.
Tetrakis(4-oxo-3,5-di-tert-butylcyclohexa-2,5-dien-1-
ylidene)tetrahydrothiophene (3)
(3) (a) Kurata, H.; Tanaka, T.; Oda, M. Chem. Lett. 1999, 28, 749.
(b) Kurata, H.; Shimoyama, T.; Matsumoto, K.; Kawase, T.; Oda,
M. Bull. Chem. Soc. Jpn. 2001, 74, 1327. (c) Kurata, H.; Takehara,
Y.; Kawase, T.; Oda, M. Chem. Lett. 2003, 32, 538. (d) Kawase, T.;
Minami, Y.; Nishigaki, N.; Okano, S.; Kurata, H.; Oda, M. Angew.
Dark-purple crystals; mp 246–248 °C (decomp.). 1H NMR (400
MHz, CDCl3): δ = 7.20 (d, J = 2.4 Hz, 2 H), 7.20 (d, J = 2.4 Hz, 2 H),
7.13 (d, J = 2.4 Hz), 7.12 (d, J = 2.4 Hz, 2 H), 1.37 (s, 18 H), 1.25 (s,
18 H), 1.24 (s, 18 H), 1.23 (s, 18 H). 13C NMR (100 MHz, CDCl3):
© Georg Thieme Verlag Stuttgart · New York — Synlett 2016, 27, A–G