Please do not adjust margins
RSC Advances
Page 9 of 11
Journal Name
DOI: 10.1039/C6RA07547A
ARTICLE
(CH), 128.2 (2 x CH), 129.1 (CH), 129.2 (CH), 130.4 (C), 130.5 research grants to PB and AG. EPC thanks the Fundação para a
(C), 133.2 (C), 152.5 (C), 152.9 (C), 168.8 (C=O).
ESI-TOF MS (m/z): 528.97 (M+1).
Ciência e a Tecnologia (FCT) for a post-doctoral research
fellowship (SFRH/BPD/72182/2010). We acknowledge project
LADECA (ALENT-07-0262-FEDER-001878) for the acquisition of
2-(2-bromo-3-methoxyphenoxy)ethyl
methoxyphenoxy)acetate (2i)
2-(2-bromo-3- the high-field NMR 400MHz Bruker Avance III machine. The
Foundation for Science and Technology (FCT) in Portugal is
Following the general procedure, compound (1i) (0.30 g, 1.22 acknowledged for funding through the strategic project PEst-
mmol), celite (1.06 g) and PCC (0.53 g, 2.45 mmol) were added OE/QUI/UI0619/2014. We thank Dr. Ricardo Mendonça
to DCM (5 mL) in a round-bottom-flask and allowed to react as (Hovione, Loures, Portugal) for useful insights and discussions
described above. After purification by silica gel on the possible oxidative esterification reaction. We also
chromatography (Hex: EtOAc (2:1)) compound
(2i) was acknowledge Dr. Kerry Gilmore from MPI for Colloids and
1
obtained as a white solid (0.136 g, 46%). H NMR (400 MHz, Interfaces in Potsdam, Germany, for facilitating HRMS analysis
CDCl3) δ: 3.87 (s, 3H, OMe), 3.89 (s, 3H, OMe), 4.23 (t, J = 4.8 of our compounds at the University of Potsdam.
Hz, 2H, CH2), 4.60 (t, J = 4.8 Hz, 2H, CH2), 4.76 (s, 2H,
CH2COOR), 6.47 (d, J = 8 Hz, 1H, ArH), 6.52 – 6.60 (m, 3H, ArH), Notes and references
7.12 (t, J = 8 Hz, 1H, ArH), 7.20 (t, J = 8 Hz, 1H, ArH). 13C NMR
(101 MHz, CDCl3) δ : 56.6 (2x OMe), 63.3 (CH2), 66.4 (CH2), 67.2
(CH2), 101.9 (CBr), 102.0 (CBr), 105.4 (CH), 105.8 (CH), 106.2
(CH), 106.4 (CH), 128.3 (CH), 128.4 (CH), 155.7 (C), 156.2 (C),
157.4 (C), 157.4 (C), 168.5 (C=O).
1
2
3
Otera, J.; Nishikido, J., “Esterification: methods, reactions,
and applications”. Wiley – VCH, Weinheim, 2nd edn. 2010
Tang, S.; Yuan, J.; Liu, C.; Lei, A. Dalton Trans. 2014, 43,
13460 – 13470.
a) Otera, J. Chem. Rev., 1993, 93, 1449 – 1470. b) Larock, R.
C. “Comprehensive organic transformations: a guide to
functional group preparations”. Wiley – VCH, New York, 2nd
.
ESI-TOF MS (m/z): 488.95 (M+1).
edn. 1999. c) Taarning, E.; Nielsen, I. S.; Egeblad, K., Madsen,
R.; Christensen, C. H. ChemSusChem. 2008, 1, 75 – 78.
a) Sarkar, S.D.; Grimme, S.; Studer, A. J. Am. Chem. Soc.,
2010, 132, 1190 – 1191. (b) Espenson, J.H.; Zhu, Z.; Zauche,
T.H. J. Org. Chem., 1999, 64, 1191–1196. (c) Gopinath, R.;
Patel, B.K. Org. Lett., 2000, 2, 577–579. (d) Maki, B.E.;
Scheidt, K.A. Org. Lett. 2008, 10, 4331–4334. (e) Gaspa, S.;
Porcheddu, A.; De Luca,L. Org. Lett. 2015, 17, 3666 - 3669
a) Tishchenko, W. J. Russ. Phys. Chem. 1906, 38, 355 and
Claisen, L. Ber. Dtsch. Chem. Ges. 1887, 20, 646-650. b)
Törmäkangas, O.P.; Koskinen, A.M.P. Rec. Res. Devel. Org.
Chem. 2001, 5, 225-255 c) Seki, T.; Nakajo, T.; Onaka, M.
Chem. Lett. 2006, 35, 824-829. d) March, J. Advanced
Organic Chemistry; Reactions, Mechanisms and Structure, 4th
ed., 1992, John Wiley & Sons Inc, New Jersey, New York. e)
Mundy, B.P.; Ellend, M.G.; Favaloro, Jr. F.G. Name Reactions
and Reagents in Organic Synthesis, 2nd Edition, 2005, John-
Wiley & Sons, Inc, New Jersey. And for some interesting
recent applications see: f) Curran, S.P.; Connon, S.J. Angew.
Chem. Int. Ed. 2012, 51, 10866-10870. g) Barman, M.K.;
Baishya, A.; Nembenna, S. J. Organomet. Chem. 2015, 785,
52-60. h) Werner, T.; Koch, J. Eur. J. Org. Chem. 2010, 6904-
6907.
a) Suzuki, T.; Matsuo, T.; Watanabe, K.; Katoh, T. Synlett,
2005, 1453–1455. (b) Liu, C.; Tang, S.; Zheng, L.; Liu, D.;
Zhang, H.; Lei, A. Angew. Chem., Int. Ed., 2012, 51, 5662-
5666. (c) Gowrisankar, S.; Neumann, H.; Beller, M. Angew.
Chem., Int. Ed., 2011, 50, 5139–5143.(d) Liu, C. ; Wang, J.;
Meng, L.; Deng, Y.; Li, Y. ; Lei, A. Angew. Chem., Int. Ed.,
2011, 50, 5144 – 5148. (e) Ray, R.; Jana, R.D.; Bhadra, M.;
Maiti, D.; Lahiri, G.K. Chem. Eur. J. 2014, 20, 15618-15624. (f)
J. Xia, A. Shao, S. Tang, X. Gao, X. Gao, A. Lei, Org. Biomol.
Chem. 2015, 13, 6154 - 6157.
2-(Phenoxy)ethyl 2-(phenoxy)acetate (2j)
4
5
Following the general procedure, compound (1j) (0.24 g, 1.76
mmol), celite (1.52 g) and PCC (0.76 g, 3.52 mmol) were added
to DCM (5 mL) in a round-bottom-flask and allowed to react as
described above. After purification by silica gel
chromatography (Hex: EtOAc (2:1)) compound
(2j) was
1
obtained as a white solid (0.161 g, 67%). H NMR (400 MHz,
CDCl3) δ: 4.2 (t, J = 4.7 Hz, 2H, CH2), 4.58 (t, J = 4.7 Hz, 2H, CH2),
4.68 (s, 2H, CH2), 6.92 (d, J = 8 Hz, 4H, ArH), 7.00 (t, J = 7 Hz,
2H, ArH), 7.29 (dd, J = 19, 8 Hz, 4H, ArH). 13C NMR (101 MHz,
CDCl3) δ: 63.6 (CH2), 65.4 (CH2), 65.7 (CH2), 114.7 (2xCH), 114.8
(2xCH), 121.4 (CH), 121.9 (CH), 129.7 (2xCH), 129.7 (2xCH),
157.9 (C), 158.4 (C), 169.0 (C=O).
Synthesis of compounds (2a) using BF3.OEt2
Alcohol derivatives (1a), (0.180 g, 1.16 mmol) were added to a
degassed round bottom flask containing dry DCM. After this,
celite (0.36 g), 1 equivalent of PCC (0.18 g, 0.83 mmol) and 1
equivalent of BF3.OEt2 (0.117 g, 0.83 mmol) were added to the
solution and the flask was degassed one more time. The
mixture was left stirring vigorously for 18h, at room
temperature, monitored by TLC. After total consumption of
the starting material, the solvent was evaporated and a
mixture of hexane/EtOAc (5:1) was added to the crude
product. This mixture was filtered over a silica pad under
vacuum. The solvent was evaporated under reduced pressure.
After purification by silica gel chromatography compounds
6
7
(a) Corey, E.J.; Suggs, J.W. Tetrahedron Lett. 1975, 31, 2647-
2650. For general information on the synthetic applications
of this reagent see: (b) Carruthers, W.; Coldham, I. Modern
methods of organic Synthesis, 4th Ed., Cambridge University
Press, 2004, Cambridge, U.K. (c) Some modern methods of
organic synthesis, Carruthers, W. 3rd Ed., Cambridge
University Press, 1987, Cambridge, U.K.
Craig, J.C.; Horning, E.C. J. Org. Chem. 1960, 25, 2098-2102.
Yunker, M.B.; Fraser-Reid, B. J.C.S. Chem. Comm. 1975, 61-
62.
(
2a), was obtained as a white solid (0.109 g, 61%). .
Acknowledgements
The authors gratefully acknowledge the following funding
sources: the INMOLFARM - Molecular Innovation and Drug
Discovery (ALENT-07-0224-FEDER-001743) of the FEDER-
INALENTEJO program including, a PhD grant to HV and
8
9
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins