Job/Unit: O42450
/KAP1
Date: 05-06-14 19:20:17
Pages: 5
D. Tanaka, S. Tanaka, A. Mori
SHORT COMMUNICATION
[2]
[3]
For reviews, see: a) T. Hama, S. Ge, J. F. Hartwig, J. Org. Chem.
2013, 78, 8250–8266; b) D. A. Culkin, J. F. Hartwig, Acc.
Chem. Res. 2003, 36, 234–245; c) C. C. C. Johansson, T. J. Col-
acot, Angew. Chem. Int. Ed. 2010, 49, 676–707; Angew. Chem.
2010, 122, 686–718.
a) C. E. Stivala, A. Zakarian, J. Am. Chem. Soc. 2011, 133,
11936–11939; b) Y. Ma, C. E. Stivala, A. M. Wright, T. Hay-
ton, J. Liang, I. Keresztes, E. Lobakovsky, D. B. Collum, A.
Zakarian, J. Am. Chem. Soc. 2013, 135, 16853–16864; see also:
c) E. M. Brun, I. Casades, S. Gil, R. Mestres, M. Parra, Tetra-
hedron Lett. 1998, 39, 5443–5446.
For examples of β-functionalization of carboxylic acid, see: a)
R. Giri, N. Maugel, J.-J. Li, D.-H. Wang, S. P. Breazzano, L. B.
Saunders, J.-Q. Yu, J. Am. Chem. Soc. 2007, 129, 3510–3511;
b) R. Giri, J.-Q. Yu, J. Am. Chem. Soc. 2008, 130, 14082–14083;
c) D.-H. Wang, T. S. Mei, J.-Q. Yu, J. Am. Chem. Soc. 2008,
130, 17676–17677; d) M. Y. Fan, D. W. Ma, Angew. Chem. Int.
Ed. 2013, 52, 12152–12155; Angew. Chem. 2013, 125, 12374–
12377.
a) A. Mori, A. Sekiguchi, K. Masui, T. Shimada, M. Horie,
K. Osakada, M. Kawamoto, T. Ikeda, J. Am. Chem. Soc. 2003,
125, 1700–1701; b) K. Masui, H. Ikegami, A. Mori, J. Am.
Chem. Soc. 2004, 126, 5074–5075; c) K. Masui, A. Mori, K.
Okano, K. Takamura, M. Kinoshita, T. Ikeda, Org. Lett. 2004,
6, 2011–2014; d) K. Kobayashi, A. Sugie, M. Takahashi, K.
Masui, A. Mori, Org. Lett. 2005, 7, 5083–5085; e) D. Mongu-
chi, T. Fujiwara, H. Furukawa, A. Mori, Org. Lett. 2009, 11,
1607–1610; f) N. Masuda, S. Tanba, A. Sugie, D. Monguchi,
N. Koumura, K. Hara, A. Mori, Org. Lett. 2009, 11, 2297–
2300; g) S. Tamba, Y. Okubo, S. Tanaka, D. Monguchi, A.
Mori, J. Org. Chem. 2010, 75, 6998–7001; h) S. Tanaka, D.
Tanaka, G. Tatsuta, K. Murakami, S. Tamba, A. Sugie, A.
Mori, Chem. Eur. J. 2013, 19, 1658–1665; i) S. Tanaka, D.
Tanaka, A. Sugie, A. Mori, Tetrahedron Lett. 2012, 53, 1173–
1176; j) S. Tanaka, S. Tamba, D. Tanaka, A. Sugie, A. Mori,
J. Am. Chem. Soc. 2011, 133, 16734–16737.
the carboxylate would also be much lower, and thereby, the
use of a Grignard reagent does not allow addition to the
carbon atom of the carbonyl group. Indeed, attempted de-
protonation of esters and ketones with tBuMgCl was found
to be ineffective.
Conclusions
In conclusion, palladium-catalyzed arylation of α-aryl-
acetic acids was found to successfully occur with several
aryl halides in a deprotonative manner to afford the di-
arylacetic acids in good to excellent yields. The deproton-
ation reaction took place with a Grignard reagent or the
combined use of a Grignard reagent with a catalytic
amount of a secondary amine and it proceeded at room
temperature to 60 °C within 3 h. It is remarkable that di-
arylacetic acids, which were prepared by arylation of related
derivatives such as esters and amides following hydrolysis,
can be obtained in the direct arylation reaction.
[4]
[5]
Experimental Section
Preparation of Bis(4-methoxyphenyl)acetic Acid (4a) as a Typical
Procedure:
A THF solution of EtMgCl (0.93 m, 1.34 mL,
1.25 mmol) was added to a solution of (4-methoxyphenyl)acetic
acid (1; 0.083 g, 0.5 mmol) in THF (1.5 mL) at room temperature.
The resulting mixture was stirred at room temperature for 3 h, and
then Pd(tBu3P)2 (5.1 mg, 0.01 mmol) was added followed by 4-
methoxy-1-bromobenzene (3a; 0.198 g, 1.0 mmol). After stirring
the mixture at 60 °C for 3 h, the resulting mixture was passed
through a pad of Celite, and the filtrate was concentrated under
reduced pressure to leave a crude oil, which was subjected to col-
umn chromatography on silica gel to afford 4a in 86% yield. 1H
NMR (300 MHz, CDCl3): δ = 3.78 (s, 6 H), 4.95 (s, 1 H), 6.86 (d, J
= 8.7 Hz, 4 H), 7.23 ppm (d, J = 8.7 Hz, 4 H). 13C NMR (75 MHz,
CDCl3): δ = 55.3, 55.5, 114.2, 129.8, 130.6, 159.0, 179.0 ppm. IR
[6] a) S. Tamba, S. Tanaka, Y. Okubo, H. Meguro, S. Okamoto,
A. Mori, Chem. Lett. 2011, 40, 398–399; b) S. Tamba, K.
Shono, A. Sugie, A. Mori, J. Am. Chem. Soc. 2011, 133, 9700–
9703; c) S. Tamba, Y. Okubo, A. Sugie, A. Mori, Polym. J.
2012, 44, 1209–1213; d) S. Tamba, K. Fuji, K. Nakamura, A.
Mori, Organometallics 2014, 33, 12–15; e) S. Tamba, K. Fuji,
H. Meguro, S. Okamoto, T. Tendo, R. Komobuchi, A. Sugie,
T. Nishino, A. Mori, Chem. Lett. 2013, 42, 281–283; f) S.
Tamba, K. Ide, K. Shono, A. Mori, Synlett 2013, 24, 1133–
1136; g) K. Nakamura, S. Tamba, A. Sugie, A. Mori, Chem.
Lett. 2013, 42, 1200–1202; h) K. Fuji, S. Tamba, K. Shono, A.
Sugie, A. Mori, J. Am. Chem. Soc. 2013, 135, 12208–12211; i)
S. Tamba, S. Mitsuda, F. Tanaka, A. Sugie, A. Mori, Organo-
metallics 2012, 31, 2263–2267; j) A. Mori, K. Ide, S. Tamba, S.
Tsuji, Y. Toyomori, T. Yasuda, Chem. Lett. 2014, DOI: org/
10.1246/cl.131222K; k) For a review: A. Mori, J. Synth. Org.
Chem. Jpn. 2011, 69, 1201–1211.
[7] PEPPSI: pyridine-enhanced precatalyst preparation stabiliza-
tion and initiation, [1,3-bis(2,6-diisopropylphenyl)imidazol-
idene] (3-chloropyridyl)palladium(II) dichloride: a) C. J.
O’Brien, E. A. B. Kantchev, C. Valente, N. Hadei, G. A. Chass,
A. Lough, A. C. Hopkinson, M. G. Organ, Chem. Eur. J. 2006,
12, 4743–4748; b) M. G. Organ, S. Calimisiz, M. Sayah, K. H.
Ho, A. J. Lough, Angew. Chem. Int. Ed. 2009, 48, 2383–2387;
Angew. Chem. 2009, 121, 2419–2423.
(ATR): ν = 2959 (br.), 2839, 1700, 1609, 1509, 1246, 1031,
˜
809 cm–1. HRMS (ESI+): calcd. for C16H15O4 [M]+ 271.0970;
found 271.0971.
Supporting Information (see footnote on the first page of this arti-
1
cle): Further experimental details and copies of the H NMR and
13C NMR spectra.
Acknowledgments
This work was partially supported by the Japan Society for the
Promotion of Science (JSPS) through Kakenhi B (grant numbers
22350042 and 25288049) and the Japanese Ministry of Education,
Culture, Sports, Science and Technology (MEXT) through Special
Coordination Funds for Promoting Science and Technology, Cre-
ation of Innovation Centers for Advanced Interdisciplinary Re-
search Areas (Innovative Bioproduction Kobe). S. T. thanks the
JSPS for a Research Fellowship for Young Scientists.
[1] a) M. Jørgensen, S. Lee, X. Liu, J. P. Wolkowski, J. F. Hartwig,
J. Am. Chem. Soc. 2002, 124, 12557–12565; b) E. T. Nadres,
G. I. F. Santosw, D. Shabashov, O. Daugulis, J. Org. Chem.
2013, 78, 9689–9714; c) Y. Aihara, N. Chatani, J. Am. Chem.
Soc. 2014, 136, 898–901; d) S. Aspin, A.-S. Goutierre, P. Larini,
R. Jazzar, O. Baudoin, Angew. Chem. Int. Ed. 2012, 51, 10808–
10811; Angew. Chem. 2012, 124, 10966–10969; e) M. V. Les-
kinen, K.-T. Yip, A. Valkonen, P. M. Pihko, J. Am. Chem. Soc.
2012, 134, 5750–5753.
[8] JohnPhos = 2-(di-tert-butylphosphanyl)biphenyl, XPhos = 2-dicy-
clohexylphosphino-2Ј,4Ј,6Ј-triisopropylbiphenyl, RuPhos = 2-di-
cyclohexylphosphino-2Ј,6Ј-diisopropoxybiphenyl, DavePhos = 2-
dicyclohexylphosphino-2Ј-(dimethylamino)biphenyl, tBuXPhos
=
2-di-tert-butylphosphino-2Ј,4Ј,6Ј-triisopropylbiphenyl; see:
C. C. Mauger, G. A. Mignani, Aldrichim. Acta 2006, 39, 17–24.
Received: April 19, 2014
Published Online:
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