7778
S. Toyota, T. Makino / Tetrahedron Letters 44 (2003) 7775–7778
9. Toyota, S.; Iida, T.; Kunizane, C.; Tanifuji, N.; Yoshida,
degassed CH3CN were added 37.8 mg (0.90 mmol) of
LiCl, 83.3 mg (0.20 mmol) of 5a, 11.6 mg (0.010 mmol)
of Pd(PPh3)4, and 79 ml (0.15 mmol) of bis(tributylstan-
nyl)ethyne. The whole was refluxed for 15 h under Ar
atmosphere. After cooling, the reaction mixture was
quenched with water, and extracted with ether. The sepa-
rated organic solution was washed with aqueous NaCl,
dried over MgSO4, and evaporated. The crude product
was purified by chromatography on silica gel to give 54
mg (96%) of 1a as orange crystal. Mp 246.0–246.5°C.
Found: C, 94.16%; H, 5.33%, calcd for C44H30: C,
94.59%; H, 5.41%. 1H NMR (CD2Cl2): l 1.12 (s, 6H),
6.29 (d, J=7.6 Hz, 4H), 7.06 (d, J=7.6 Hz, 4H), 7.22
(dd, J=1.3, 6.7 Hz, 2H), 7.43–7.55 (m, 6H), 8.01–8.04
(m, 4H), 8.38 (dd, J=1.2, 8.7 Hz, 2H), 8.44 (s, 2H).
18. A weak emission (uem 500 nm) was observed in the
fluorescence spectra of 1, its intensity being much lower
than that of the reference compound 2.
Y. Org. Biomol. Chem. 2003, 1, 2298–2302.
10. Bedard, T. C.; Moore, J. S. J. Am. Chem. Soc. 1995, 117,
10662–10671.
(
11. (a) Toyota, S.; Yamamori, T.; Asakura, M.; Oki, M.
Bull. Chem. Soc. Jpn. 2000, 73, 205–213; (b) Toyota, S.;
(
Yamamori, T.; Makino, T.; Oki, M. Bull. Chem. Soc.
Jpn. 2000, 73, 2591–2597; (c) Toyota, S.; Yamamori, T.;
Makino, T. Tetrahedron 2001, 57, 3521–3528.
12. Koo Tze Mew, P.; Vo¨gtle, F. Angew. Chem., Int. Ed.
Engl. 1979, 18, 159–161.
13. (a) Akiyama, S.; Nakasuji, K.; Nakagawa, M. Bull.
Chem. Soc. Jpn. 1971, 44, 2231–2236; (b) Pschirer, N. G.;
Bunz, U. H. F. Tetrahedron Lett. 1999, 40, 2481–2484; (c)
Wadsworth, D. H.; Donatelli, B. A. Synthesis 1981,
285–286.
14. Becker, H. D.; Skelton, B. W.; White, A. H. Aust. J.
Chem. 1985, 38, 1567–1570.
15. Triflates 5 are useful precursors and a source of substi-
tuted 9-anthryl groups for various coupling reactions.
Akiba et al. reported the synthesis of 9-TfO-1,8-
dimethoxyanthracene from the corresponding 9-hydroxy-
anthracene under the condition of NaH+Tf2O/THF;
however, this protocol gave a poor result for ordinary
9-anthrones. See, Akiba, K.-y.; Yamashita, M.;
Yamamoto, Y.; Nagase, S. J. Am. Chem. Soc. 1999, 121,
10644–10645. A typical procedure of synthesis of 5: To a
solution of 2.70 g (9.50 mmol) of 4a in 120 ml of dry
CH2Cl2 were added 3.0 ml of HMPA and 15 ml of a
solution of LiHMDS in THF (1.0 mol l−1) at −78°C
under an Ar atmosphere. The solution was stirred for 2 h
below −70°C, to which 1.62 ml (9.60 mmol) of Tf2O was
added slowly. The reaction mixture was stirred for 12 h
at the temperature, warmed up to room temperature, and
then quenched with water. The organic materials were
extracted with CH2Cl2. The organic layer was dried over
MgSO4, and evaporated. The crude product was purified
by chromatography on silica gel with hexane–CH2Cl2
(1:1) eluent to give 2.95 g (74%) of 5a as pale yellow
solid. Mp 125.5–127.5°C (dec); Found FAB: M+
19. Crystallographic data for 1a: C44H30, FW 558.72, mono-
,
clinic, C2/c, a=26.905(1), b=14.784(2), c=15.660(2) A,
3
,
i=108.610(6)°, V=5903.4(10) A , Z=8, Dcalcd=1.257 g
cm−3
,
R=0.070, Rw=0.111. Crystallographic data
(excluding structure factors) for the structure, have been
deposited with the Cambridge Crystallographic Data
Centre as supplementary publication numbers CCDC
213941. Copies of the data can be obtained, free of
charge, on application to CCDC, 12 Union Road, Cam-
bridge CB2 1EZ, UK (Fax: +44(0)-1223-336033 or e-
mail: deposit@ccdc.cam.ac.uk).
20. The 13C NMR signal due to sp carbons was observed at
ca. l 104 for 1 (cf. l 97.4 for 2). This deshielding is partly
attributed to the bending deformation.
21. Total lineshape analysis was performed using the
DNMR3K program, which is a modified version of the
DNMR3 program. (a) Binsch, G. Top. Stereochem. 1968,
3, 97–192; (b) Kleier, D.; Binsch, G. QCPE c165, Indi-
ana University, Bloomington, IN, USA.
22. As for acyclic dialkylethynes, the highest barrier was
recorded by (1,4-dimethyl-9-triptycyl)(1-mesityl-9-trip-
tycyl)ethyne at 18.8 kcal mol−1. See Ref. 11c.
1
416.0673, calcd for C22H15O3F3S: M 416.0694; H NMR
23. One example of a similar dynamic behavior is the
diastereomerization of 1,8-bis(3-substituted phenyl)-
naphthalenes via the rotation of phenyl groups (barrier:
15–16 kcal mol−1). House, H. O.; Campbell, W. J.; Gall,
M. J. Org. Chem. 1970, 35, 1815–1819.
24. Strictly, this point should be discussed on the basis of the
correlated rotation. At present, the extent of correlation
is unclear from available data.
(CDCl3): l 2.46 (s, 3H), 7.28 (d, J=7.8 Hz, 2H), 7.39
(brs, 2H), 7.49–7.62 (m, 4H), 7.99 (d, J=8.3 Hz, 1H),
8.05 (d, J=8.1 Hz, 1H), 8.19 (d, J=8.6 Hz, 1H), 8.55 (s,
1H).
16. Cummins, C. H. Tetrahedron Lett. 1994, 35, 857–860.
1
17. Compounds 1a–d were satisfactorily identified by H, 13C
NMR and mass spectroscopies as well as microanalysis.
A typical procedure of synthesis of 1: To 5 ml of