down to room temperature, treated with saturated aq. NH4Cl
and extracted with EtOAc. The extract was washed with brine
and dried over MgSO4. The solvent was removed under
reduced pressure and the crude product purified by silica gel
column chromatography (2% EtOAc–hexane) to give 59.4 mg
(yield, 81%) of 7ns. Recrystallized from hexane–chloroform,
colorless needles, mp 105 1C. Anal. calc. for C20H16O: C,
3 (a) F. W. Bailey and R. E. Punzalan, J. Org. Chem., 1990, 55, 5404;
(b) E. C. Tucker, N. T. Majid and P. Knochel, J. Am. Chem. Soc.,
1992, 114, 3983.
4 (a) Y. Kondo, H. Shilai, M. Uchiyama and T. Sakamoto, J. Am.
Chem. Soc., 1999, 121, 3539; (b) T. Imahori, M. Uchiyama and
Y. Kondo, Chem. Commun., 2001, 2450; (c) P. F. H. Schwab,
F. Fleischer and J. Michl, J. Org. Chem., 2002, 67, 443;
(d) M. Uchiyama, T. Miyoshi, Y. Kajihara, T. Sakamoto,
Y. Otani, T. Ohwada and Y. Kondo, J. Am. Chem. Soc., 2002,
124, 8514; (e) M. Uchiyama, Y. Matsumoto, D. Nobuto,
T. Furuyama, K. Yamaguchi and K. Morokuma, J. Am. Chem.
Soc., 2006, 128, 8748; (f) Y. Kondo, J. V. Morey, J. C. Morgan,
H. Naka, D. Nobuto, P. R. Raithby, M. Uchiyama and A. E.
H. Wheatley, J. Am. Chem. Soc., 2007, 129, 12734; (g) D. Nobuto
and M. Uchiyama, J. Org. Chem., 2008, 73, 1117;
(h) M. Uchiyama, Y. Kobayashi, T. Furuyama, S. Nakamura,
Y. Kajihara, T. Miyoshi, T. Sakamoto, Y. Kondo and
K. Morokuma, J. Am. Chem. Soc., 2008, 130, 472.
5 (a) E. Hevia, G. W. Honeyman and R. E. Mulvey, J. Am. Chem.
Soc., 2005, 127, 13106; (b) W. Clegg, S. H. Dale, R. W. Harrington,
E. Hevia, G. W. Honeyman and R. E. Mulvey, Angew. Chem., Int.
Ed., 2006, 45, 2374; (c) W. Clegg, S. H. Dale, A. M. Drummond,
E. Hevia, G. W. Honeyman and R. E. Mulvey, J. Am. Chem. Soc.,
2006, 128, 7434; (d) D. R. Armstrong, W. Clegg, S. H. Dale,
E. Hevia, L. M. Hogg, G. W. Honeyman and R. E. Mulvey,
Angew. Chem., Int. Ed., 2006, 45, 3775; (e) R. E. Mulvey,
F. Mongin, M. Uchiyama and Y. Kondo, Angew. Chem., Int.
Ed., 2007, 46, 3802; (f) W. Clegg, B. Conway, E. Hevia,
M. D. McCall, L. Russo and R. E. Mulvey, J. Am. Chem. Soc.,
2009, 131, 2375; (g) A. R. Kennedy, J. Klett, R. E. Mulvey and
D. S. Wright, Science, 2009, 326, 706.
6 (a) M. L. Hlavinka and J. R. Hagadorn, Tetrahedron Lett., 2006,
47, 5049; (b) S. H. Wunderlich and P. Knochel, Angew. Chem., Int.
Ed., 2007, 46, 7685; (c) A. Seggio, F. Chevallier, M. Vaultier and
F. Mongin, J. Org. Chem., 2007, 72, 6602; (d) M. Mosrin
and P. Knochel, Chem.–Eur. J., 2009, 15, 1468; (e) M. Mosrin
and P. Knochel, Org. Lett., 2009, 11, 1837.
7 (a) N. Boudet, S. Sase, P. Sinha, C.-Y. Liu, A. Krasovskiy and
P. Knochel, J. Am. Chem. Soc., 2007, 129, 12358; (b) S. Sase,
M. Jaric, A. Metzger, V. Malakhov and P. Knochel, J. Org. Chem.,
2008, 73, 7380; (c) A. Krasovskiy, C. Duplais and B. H. Lipshutz,
J. Am. Chem. Soc., 2009, 131, 15592; (d) C.-Y. Liu, X. Wang,
T. Furuyama, S. Yasuike, A. Muranaka, K. Morokuma and
M. Uchiyama, Chem.–Eur. J., 2010, 16, 1780.
1
88.20; H, 5.92; O, 5.87; found: C, 88.24; H, 6.24%. H NMR
(400 MHz, CDCl3/TMS) d (ppm): 2.60 (s, 3H), 4.03 (s, 3H),
7.28 (d, J = 2.7 Hz, 1H) 7.42 (d, J = 8.5 Hz, 1H), 7.60–7.66
(m, 2H), 8.05 (d, J = 2.7 Hz, 1H), 8.35 (s, 1H), 8.50–8.63 (m,
4H). 13C{1H}NMR (100 MHz, CDCl3) d (ppm): 22.0, 55.5,
105.6, 115.6, 122.6, 123.0, 123.1, 123.2 123.5, 124.7, 126.3,
126.4, 127.1, 127.6, 128.9, 129.7, 130.1, 131.2, 136.7, 158.5.
LRMS (EI) m/z: 272 (M+). HRMS: calc. for C20H16O:
272.1201; found: 272.1178. IR(neat): 2989, 2912, 1611, 1507,
1422, 1301, 1233, 1206, 1173, 1057, 1034, 850.9, 758.3 cmꢁ1
.
7nt. Yield: 58%, recrystallized from hexane–chloroform,
colorless needles, mp 126 1C. Anal. calc. for C20H16O2: C,
83.31; H, 5.59; O, 11.10; found: C, 83.19; H, 5.80%. 1H NMR
(400 MHz, CDCl3/TMS) d (ppm): 4.01 (s, 3H), 4.03 (s, 3H),
7.20–7.27 (m, 2H) 7.58–7.65 (m, 2H), 7.94 (d, J = 2.7 Hz, 1H),
8.03 (d, J = 2.7 Hz, 1H), 8.47–8.55 (m, 4H). 13C{1H}NMR
(100 MHz, CDCl3) d (ppm): 55.4, 55.5, 105.2, 105.6, 114.7,
115.6, 122.6, 122.7, 123.1, 123.3, 124.7, 124.8, 125.9, 127.2,
128.3, 130.2, 131.2, 131.5, 158.6, 158.7. LRMS (EI) m/z: 288
(M+). HRMS: calc. for C20H16O2: 288.1150; found: 288.1129.
IR(neat): 2923, 1725, 1613, 1449, 1210, 1181, 1042, 808.5,
746.7, 702.3 cmꢁ1
.
7us. Yield: 70%, recrystallized from hexane–chloroform,
colorless needles, mp 180–181 1C. Anal. calc. for C20H16O2:
C, 77.41; H, 4.22; F, 18.37; found: C, 77.70; H, 4.21%. 1H
NMR (400 MHz, CDCl3/TMS) d (ppm): 2.65 (s, 3H), 7.54 (d,
J = 8.5 Hz, 1H), 7.69 (m, 2H), 7.85 (d, J = 8.5 Hz, 1H), 8.42
(s, 1H), 8.55 (d, J = 8.8 Hz, 1H), 8.62–8.64 (m, 2H), 8.73
(d, J = 8.8 Hz, 1H), 8.88 (s, 1H). 13C{1H}NMR (100 MHz,
CDCl3) d (ppm): 21.9, 120.6, 120.9, 123.1 (2C), 123.2, 123.6,
123.9, 126.9, 127.6, 128.1, 128.2, 128.4, 128.8 (2C), 129.4 (2C),
130.4, 132.2, 137.3. LRMS (EI) m/z: 310 (M+). HRMS: calc.
for C20H13F3: 310.0969; found: 310.0979. IR(neat): 2923,
8 (a) P. Knochel and R. D. Singer, Chem. Rev., 1993, 93, 2117 and
references therein; (b) Y. Kondo, N. Takazawa, C. Yamazaki and
T. Sakamoto, J. Org. Chem., 1994, 59, 4717; (c) M. Uchiyama,
M. Kameda, O. Mishima, N. Yokoyama, M. Koike, Y. Kondo
and T. Sakamoto, J. Am. Chem. Soc., 1998, 120, 4934;
(d) M. Uchiyama, T. Furuyama, M. Kobayashi, Y. Matsumoto
and K. Tanaka, J. Am. Chem. Soc., 2006, 128, 8404;
(e) T. Furuyama, M. Yonehara, S. Arimoto, M. Kobayashi,
Y. Matsumoto and M. Uchiyama, Chem.–Eur. J., 2008, 14,
10348; (f) F. F. Kneisel, M. Dochnahl and P. Knochel, Angew.
Chem., Int. Ed., 2004, 43, 1017; (g) L.-Z. Gong and P. Knochel,
Synlett, 2005, 267.
1725, 1320, 1279, 1111, 1081, 812.3, 762.2, 717.8, 698.5 cmꢁ1
.
9 (a) For instance, in the catalytic asymmetric arylation of aldehydes
using arylzinc reagents developed by Walsh et al., lithium chloride,
formed en route to arylzinc reagents, caused background reactions,
forming racemic products. They found that the addition of
tetraethylenediamine (TEEDA) to the reaction mixture was
effective for suppressing the background reaction promoted by
the lithium salt, and this protocol enabled the asymmetric arylation
of aldehydes with high enantioselectivity without filtration of the
lithium salt (J. G. Kim and P. J. Walsh, Angew. Chem., Int. Ed.,
2006, 45, 4175; L. Salvi, S.-J. Jeon, E. L. Fisher, P. J. Carroll and
P. J. Walsh, J. Am. Chem. Soc., 2007, 129, 16119). (b) Removal of
these metal salts was not easy because arylzinc species are air and
moisture sensitive (J. Rudolph, N. Hermanns and C. Bolm, J. Org.
Chem., 2004, 69, 3997; B. Weber and D. Seebach, Tetrahedron,
1994, 50, 7473).
Acknowledgements
This work was partly supported by a Grant-in-Aid for Young
Scientists (B) from the Ministry of Education, Culture, Sports,
Science and Technology, Japan (to H. N., no. 19790003) and
by Grants-in-Aid for Scientific Research on Priority Areas
‘‘Advanced Molecular Transformation of Carbon Resources’’,
‘‘Synergistic Effects for Creation of Functional Molecules’’
(to Y. K.).
References
10 (a) R. Schwesinger and H. Schlemper, Angew. Chem., Int. Ed.
Engl., 1987, 26, 1167; (b) R. Schwesinger, H. Schlemper,
C. Hasenfratz, J. Willaredt, T. Dambacher, T. Breuer,
C. Ottaway, M. Fletscinger, J. Boele, H. Fritz, D. Putzas,
1 P. Knochel and P. Jones, Organozinc Reagents, Oxford University
Press, Oxford, 1999.
2 P. Knochel and R. D. Singer, Chem. Rev., 1993, 93, 2117.
ꢀc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2010 New J. Chem., 2010, 34, 1700–1706 | 1705