E
N. Miyamoto et al.
Letter
Synlett
Funding Information
J. Am. Chem. Soc. 2008, 130, 17320. (c) Kim, Y.-H.; Shin, D.-C.;
Kim, S.-H.; Ko, C.-H.; Yu, H.-S.; Chae, Y.-S.; Kwon, S.-K. Adv.
Mater. 2001, 13, 1690.
This work was financially supported by JSPS KAKENHI Grant Num-
bers 16H01127, 16H00999, 17K05773, 16K04864, a Grant-in aid for
Scientific Research (A) (26253001), JST ERATO (JPMJER1301), MEXT
(Interdepartmental Doctoral Degree Program for Multidimensional
(14) (a) Clososki, G. C.; Rohbogner, C. J.; Knochel, P. Angew. Chem. Int.
Ed. 2007, 46, 7681. (b) Rohbogner, C. J.; Clososki, G. C.; Knochel,
P. Angew. Chem. Int. Ed. 2008, 47, 1503. (c) Rohbogner, C. J.;
Wagner, A. J.; Clososki, G. C.; Knochel, P. Org. Synth. 2009, 86,
374.
Material Science Leaders), and JSPS predoctoral fellowship (for N.M.).SKJPSA
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(15) (a) Okano, K.; Fujiwara, H.; Noji, T.; Fukuyama, T.; Tokuyama, H.
Angew. Chem. Int. Ed. 2010, 49, 5925. (b) Tokuyama, H.; Okano,
K.; Fujiwara, H.; Noji, T.; Fukuyama, T. Chem. Asian J. 2011, 6,
560. (c) Noji, T.; Fujiwara, H.; Okano, K.; Tokuyama, H. Org. Lett.
2013, 15, 1946. (d) Noro, T.; Okano, K.; Tokuyama, H. Synlett
2013, 24, 2143. For a construction of the pyrroloquinoline skele-
ton using the benzyne-mediated strategy, see: (e) Oshiyama, T.;
Satoh, T.; Okano, K.; Tokuyama, H. RSC Adv. 2012, 2, 5147.
(f) Oshiyama, T.; Satoh, T.; Okano, K.; Tokuyama, H. Tetrahedron
2012, 68, 9376.
(16) (a) Momoi, Y.; Okano, K.; Tokuyama, H. Synlett 2014, 25, 2503.
(b) Sun, Z.; Miyamoto, N.; Sato, S.; Tokuyama, H.; Isobe, H.
Chem. Asian J. 2017, 12, 271.
(17) A preliminary result of [4+2] cycloaddition of 1,3-(4-bromophe-
nyl)isobenzofuran with benzyne generated by treatment of
PhOTf with Mg(TMP)2·2LiCl was reported by our group (ref.
16b).
Supporting Information
Supporting information for this article is available online at
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References and Notes
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(18) A Gram-Scale Preparation of tert-Butyl 9,10-Diphenyl-9,10-
epoxy-2-anthracenecarboxylate (3e)
A flame-dried 500 mL three-necked round-bottomed flask
equipped with a 200 mL dropping funnel, a magnetic stirring
bar, a rubber septum, and an inlet adapter with a three-way
stopcock was charged with 1,3-diphenylisobenzofuran (2a, 2.16
g, 8.00 mmol), dry THF (20.0 mL), and tert-butyl 4-(trifluoro-
methylsulfonyloxy)benzoate (1e, 1.23 g, 3.77 mmol). After
cooling to –78 °C, Mg(TMP)2·2LiCl (0.16 M in THF, 130 mL, 20
mmol) was added dropwise to the flask, and the resulting
mixture was stirred at –78 °C for 1 h. The flask was then
immersed in an ice bath, and the mixture was stirred for 11 h,
after which time TLC (hexanes–EtOAc = 2:1) indicated complete
consumption of tert-butyl 4-(trifluoromethylsulfonyloxy)ben-
zoate (1e). The reaction was quenched by addition of sat. aq
NH4Cl, and the aqueous layer was extracted with EtOAc three
times. The combined organic extracts were successively washed
with H2O and brine, dried over anhydrous Na2SO4, and filtered.
The organic solvents were removed under reduced pressure to
give a crude epoxyanthracene, which was purified by flash
column chromatography on silica gel (hexanes–dichlorometh-
ane = 1:1) to afford 3e (1.53 g, 3.43 mmol, 91%) as a white solid.
Rf = 0.18 (hexanes–dichloromethane = 1:1). The spectral data of
3e were in complete agreement with those reported in the liter-
ature (ref. 19).
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Shanmugaraja, M. Synthesis 2013, 45, 2913. (d) Hoffend, C.;
Diefenbach, M.; Januszewski, E.; Bolte, M.; Lerner, H.-W.;
Holthausen, M. C.; Wagner, M. Dalton Trans. 2013, 42, 13826.
(e) Serevicius, T.; Komskis, R.; Adoménas, P.; Adoméniené, O.;
Jankauskas, V.; Gruodis, A.; Kazlauskas, K.; Jursénas, S. Phys.
Chem. Chem. Phys. 2014, 16, 7089.
(19) Uchiyama, M.; Kobayashi, Y.; Furuyama, T.; Nakamura, S.;
Kajihara, Y.; Miyoshi, T.; Sakamoto, T.; Kondo, Y.; Morokuma, K.
J. Am. Chem. Soc. 2008, 130, 472.
(20) Wardrop, D. J.; Burge, M. S. Chem. Commun. 2004, 1230.
(21) tert-Butyl 9,10-Diphenyl-2-anthracenecarboxylate (4e)
A 10 mL test tube equipped with a magnetic stirring bar and a
cap was charged with tert-butyl 9,10-diphenyl-9,10-epoxy-2-
anthracenecarboxylate (3e, 100 mg, 224 μmol), wet CH2Cl2 (448
μL), Et3SiH (53.7 μL, 336 μmol), and TFA (20.0 μL, 269 μmol). The
mixture was stirred for 23 h, after which time TLC (hexanes–
EtOAc = 3:1) indicated complete consumption of tert-butyl
9,10-diphenyl-9,10-epoxy-2-anthracenecarboxylate (3e). The
reaction was quenched by addition of H2O, and the aqueous
(13) (a) Lyu, Y.-Y.; Kwak, J.; Kwon, O.; Lee, S.-H.; Kim, D.; Lee, C.;
Char, K. Adv. Mater. 2008, 20, 2720. (b) Moorthy, J. N.;
Venkatakrishnan, P.; Natarajan, P.; Huang, D.-F.; Chow, T. J.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–F