1
867
Synthesis
W. Han et al.
Paper
1
H NMR (400 MHz, CDCl ): δ = 7.89 (d, J = 8.0 Hz, 1 H), 7.39–7.35 (m, 1
References
3
H), 7.23–7.21 (m, 2 H), 4.28 (t, J = 6.0 Hz, 2 H), 2.58 (s, 3 H), 1.78–1.71
(
1) (a) Larghi, E. L.; Operto, M. A.; Torres, R.; Kaufman, T. S. Bioorg.
Med. Chem. Lett. 2009, 19, 6172. (b) Navarro, I.; Pöverlein, C.;
Schlingmann, G.; Barrett, A. G. M. J. Org. Chem. 2009, 74, 8139.
(m, 2 H), 1.42–1.36 (m, 4 H), 0.91 (t, J = 6.0 Hz, 3 H).
13
C NMR (100 MHz, CDCl ): δ = 67.8, 140.0, 131.8, 131.6, 130.5, 129.9,
3
1
25.6, 64.9, 28.4, 28.2, 22.3, 21.7, 14.0.
(c) Maag, H. Prodrugs of Carboxylic Acids, In Prodrugs; Vol. V;
Stella, V.; Borchardt, R.; Hageman, M.; Oliyai, R.; Maag, H.; Tilley,
J., Eds.; Springer: New York, 2007, 703. (d) Bew, S. P. Carboxylic
Acids, In Comprehensive Organic Functional Group Transforma-
tions II; Katritzky, A. R.; Taylor, R. J. K., Eds.; Elsevier: Oxford,
4
-Fluorobenzyl 4-Methoxybenzoate (3q)
[
CAS Reg. No.: 142599-45-9]
A 25-mL flask was charged with Pd(OAc)2 (1.2 mg, 0.005 mmol), 1q
119 mg, 0.5 mmol), K CO (211.5 mg, 1.5 mmol), H O (0.5 mL), and
2005, 19. (e) Ogliaruso, M. A.; Wolfe, J. F. Synthesis of Carboxylic
(
2
3
2
Acids, Esters, and Their Derivatives; Patai, S.; Rappoport, Z., Eds.;
Wiley: New York, 1991.
2) (a) Ueda, T.; Konishi, H.; Manabe, K. Org. Lett. 2012, 14, 3100.
PEG 400 (2.0 mL). The flask was subjected to standard cycles (3 ×) of
evacuation and back-filling with dry and pure CO. The mixture was
stirred at r.t. for 5 h. Then, 4-fluorobenzyl chloride (122 μL, 1.0 mmol)
was added to the mixture and it was stirred at 80 °C for a further 24 h.
The mixture was cooled to r.t., poured into sat. aq NaCl (15 mL), and
(
(
(
b) Ueda, T.; Konishi, H.; Manabe, K. Org. Lett. 2012, 14, 5370.
c) Gadakh, A. V.; Dinesh, C.; Rindhe, S. S.; Karale, B. K. Synth.
Commun. 2012, 42, 658. (d) Schareina, T.; Zapf, A.; Cotte, A.;
Gotta, M.; Beller, M. Adv. Synth. Catal. 2010, 352, 1205.
extracted with Et O (3 × 15 mL). The solvent was removed from the
organic phases on a rotary evaporator. The crude product was puri-
2
(e) Berger, P.; Bessmernykh, A.; Caille, J.-C.; Mignonac, S. Syn-
fied by column chromatography (silica gel, PE–EtOAc–HCO H, 25:1:1)
2
thesis 2006, 3106. (f) Lesma, G.; Sacchetti, A.; Silvani, A. Synthe-
sis 2006, 594. (g) Morimoto, T.; Kakiuchi, K. Angew. Chem. Int.
Ed. 2004, 43, 5580. (h) Cacchi, S.; Fabrizi, G.; Goggiamani, A. Org.
Lett. 2003, 5, 4269. For examples of Pd-catalyzed carbonylation
with alkyl formate, see: (i) Ko, S.; Lee, C.; Choi, M. G.; Na, Y.;
Chang, S. J. Org. Chem. 2003, 68, 1607. (j) Carpentier, J. F.;
Castanet, Y.; Brocard, J.; Mortreux, A.; Petit, F. Tetrahedron Lett.
to afford 3q (105 mg, 81%) as a white solid; mp 54.6–55.1 °C.
1
H NMR (400 MHz, CDCl ): δ = 8.0 (d, J = 8.0 Hz, 2 H), 7.41 (m, 2 H),
3
7.05 (t, J = 8.0 Hz, 2 H), 6.89 (t, J = 8.0 Hz, 2 H), 5.28 (s, 2 H), 3.83 (s, 3
H).
13
C NMR (100 MHz, CDCl ): δ = 166.1, 163.5, 162.6 (d, J = 245 Hz),
3
132.1 (d, J = 3 Hz), 131.7, 130.1 (d, J = 8 Hz), 122.4, 115.5 (d, J = 22 Hz),
113.6, 65.7, 55.4.
1991, 32, 4705. (k) Pri-Bar, I.; Buchman, O. J. Org. Chem. 1988,
53, 624.
Mercury(0) Poisoning Test
(3) For recent reviews, see ref. 2f and:Odell, L. R.; Russo, F.; Larhed,
M. Synlett 2012, 685.
The reaction of Pd(OAc)2 (2.4 mg, 0.01 mmol), 1a (127.0 mg, 0.5
(
4) Friis, S. D.; Andersen, T. L.; Skrydstrup, T. Org. Lett. 2013, 15,
378.
mmol), K CO (141.0 mg, 1.0 mmol), and H O (0.5 mL) in PEG 400 (2.0
2
3
2
1
mL) was performed with the addition of elemental mercury (200.6
mg, 1 mmol, 100 equiv) (relative to Pd). After 2 h at r.t., the yield of the
product 2a was 67 mg (80%), suggesting that the reaction is not af-
fected by the introduction of Hg(0).
(
5) For some recent reviews on Pd-catalyzed carbonylations of aryl
halides with CO, see: (a) Gadge, S. T.; Bhanage, B. M. RSC Adv.
2014, 4, 10367. (b) Fang, W.; Zhu, H.; Deng, Q.; Liu, S.; Liu, X.;
Shen, Y.; Tu, T. Synthesis 2014, 46, 1689. (c) Wu, X.-F.; Neumann,
H.; Beller, M. Chem. Rev. 2013, 113, 1. (d) Wu, X.-F.; Beller, M.
Transition Metal Catalyzed Carbonylation Reactions-Carbonyla-
tive Activation of C–X Bonds; Springer: Heidelberg, 2013.
Carbon Disulfide Poisoning Test (Table 4)
Following the typical procedure, four reactions of Pd(OAc)2 (2.4 mg,
0
.01 mmol), 1a (127.0 mg, 0.5 mmol), K CO (141.0 mg, 1.0 mmol),
2 3
(
4
(
(
e) Wu, X.-F.; Neumann, H.; Beller, M. Chem. Soc. Rev. 2011, 40,
986. (f) Magano, J.; Dunetz, J. R. Chem. Rev. 2011, 111, 2177.
g) Grigg, R.; Mutton, S. P. Tetrahedron 2010, 66, 5515.
h) Brennfuhrer, A.; Neumann, H.; Beller, M. Angew. Chem. Int.
and H O (0.5 mL) in PEG 400 (2.0 mL) were performed, one as a con-
2
trol. To the three other reactions was added CS (0.65 equiv, 1.0 equiv,
2
and 1.5 equiv, relative to Pd). All reaction mixtures were stirred at r.t.
for 2 h. The corresponding yields of 2a were 75 mg, 4.2 mg, and only a
trace amount.
Ed. 2009, 48, 4114. Other reviews on carbonylation with CO,
see: (i) Wu, L. P.; Fang, X. J.; Liu, Q.; Jackstell, R.; Beller, M.; Wu,
X.-F. ACS Catal. 2014, 4, 2977. (j) Wu, X.-F.; Fang, X. J.; Wu, L. P.;
Jackstell, R.; Neumann, H.; Beller, M. Acc. Chem. Res. 2014, 47,
Acknowledgment
1
2
4
041. (k) Wu, X.-F.; Neumann, H.; Beller, M. ChemSusChem
013, 6, 229. (l) Wu, X.-F.; Neumann, H. ChemCatChem 2012, 4,
47.
The work was sponsored by the Natural Science Foundation of China
(
(
21302099), the Natural Science Foundation of Jiangsu Province
BK2012449), the Natural Science Foundation of Jiangsu Provincial
(
6) (a) Tsai, S. W.; Huang, S. H.; Lee, H. S.; Tsai, F. Y. J. Chin. Chem.
Soc. 2013, 60, 769. (b) Xue, L. Q.; Shi, L. J.; Han, Y.; Xia, C. G.;
Huynh, H. V.; Li, F. W. Dalton Trans. 2011, 40, 7632.
Colleges and Universities (12KJB150014), the Scientific Research
Start-up Foundation of Nanjing Normal University
2011103XGQ0250), the SRF for ROCS, SEM, and the Priority Academ-
(c) Wittmann, S.; Schätz, A.; Grass, R. N.; Stark, W. J.; Reiser, O.
(
Angew. Chem. Int. Ed. 2010, 49, 1867. (d) Cacchi, S.; Cotet, C. L.;
Fabrizi, G.; Forte, G.; Goggiamani, A.; Martín, L.; Martínez, S.;
Molins, E.; Moreno-Mañas, M.; Petrucci, F.; Roig, A.; Vallribera,
A. Tetrahedron 2007, 63, 2519. (e) Mizushima, E.; Hayashi, T.;
Tanaka, M. Top. Catal. 2004, 29, 163. (f) Calò, V.; Giannoccaro, P.;
Nacci, A.; Monopoli, A. J. Organomet. Chem. 2002, 645, 152.
ic Program Development of Jiangsu Higher Education Institutions.
Supporting Information
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0034-1380497.
(g) Cheprakov, A. V.; Ponomareva, N. V.; Beletskaya, I. P.
S
u
p
p
ortioIgnfrm oaitn
S
u
p
p
ortioIgnfrm oaitn
J. Organomet. Chem. 1995, 486, 297. (h) Bumagin, N. A.; Nikitin,
K. V.; Beletskaya, I. P. J. Organomet. Chem. 1988, 358, 563.
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 1861–1868