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Cu (Otf) - Mediated Chan-Lam Reaction of Carboxylic Acids To Access Phenolic Esters
Cu (Otf) - Mediated Chan-Lam Reaction of Carboxylic Acids To Access Phenolic Esters
org/joc
7472 J. Org. Chem. 2010, 75, 7472–7474 Published on Web 10/13/2010 DOI: 10.1021/jo101558s
r 2010 American Chemical Society
Zhang et al.
JOC Note
TABLE 1. Selected Results for Optimal Reaction Conditionsa TABLE 2. Reaction of Carboxylic Acids with Phenylboronic Acida
TABLE 3. Reaction of Benzoic Acid with Arylboronic Acidsa The phenol was detected as a byproduct during the
procedure. However, when benzoic acid and phenol were
subjected to the standard reaction condition in the absence
or presence of phenylboronic acid (10 and 20 mol %, respec-
tively), a trace of ester (<1%) was formed. This result ruled
out the possibility of a hydroxylation of boronic acids9/
esterification pathway.
In conclusion, we have developed a Cu(OTf)2-mediated
Chan-Lam reaction of carboxylic acid and arylboronic acids,
affording the phenolic esters in moderate to good yields. The
reaction showed remarkably broad substrate scope and good
functional group tolerance.
Experimental Section
Typical Experimental Procedure for the Reaction of Arylboron-
ic Acids with Carboxylic Acids to Esters. Under air, a reaction
tube was charged with carboxylic acid (0.2 mmol), arylboronic
acid (0.6 mmol), Cu(OTf)2 (29 mg, 40 mol %), urea (0.2 mmol),
and ethyl acetate (2 mL). The mixture was stirred at 60 °C. After
the mixture was kept stirring for 12 or 24 h, the solvent was
evaporated under reduced pressure and the residue was purified
by flash column chromatography on silica gel to give the product.
Phenyl 2-Acetoxybenzoate (3ma). Compound 3ma is a white
solid; 1H NMR (CDCl3, 500 MHz): δ 8.15 (d, J = 7.9 Hz, 1H),
7.58-7.54 (m, 1H), 7.36-7.31 (m, 3H), 7.21-7.17 (m, 1H),
7.11-7.09 (m, 3H), 2.23 (s, 3H). 13C NMR (CDCl3, 125 MHz): δ
169.7, 162.9, 151.2, 150.6, 134.5, 132.2, 129.5, 126.1, 126.0,
124.0, 121.7, 21.0. IR (prism, cm-1): 3058, 1739, 1694, 1483,
1188, 740. MS (EI) 256 (Mþ); HRMS Calcd for C15H12O4 (Mþ),
256.0736; found, 256.0730.
Acknowledgment. We thank the National Natural Science
Foundation of China (No. 20972115), the Key Project of
Chinese Ministry of Education (No. 209054), and State Key
Laboratory of Coordination Chemistry of Nanjing Univer-
sity for financial support.
Supporting Information Available: Experimental proce-
dures along with copies of spectra. This material is available
free of charge via the Internet at http://pubs.acs.org.
a
Reaction conditions: benzoic acid (24 mg, 0.2 mmol), arylboronic
acid (0.6 mmol), Cu(OTf)2 (29 mg, 40 mol %), urea (12 mg, 1.0 equiv) in (9) The transition-metal catalyzed hydroxylation of boronic acids, please
see: (a) Xu, J.; Wang, X.; Shao, C.; Su, D.; Cheng, G.; Hu, Y. Org. Lett. 2010,
EtOAc (2 mL), 60 °C, 24 h, under air. 12, 1964. (b) Kianmehr, E.; Yahyaee, M.; Tabatabai, K. Tetrahedron Lett.
2007, 48, 2713. (c) Maleczka, R. E.; Shi, F.; Holmes, D.; Smith,
phenylboronic such as 2-chlorophenylboronic, 2-methoxy- M. R., III. J. Am. Chem. Soc. 2003, 125, 7792. (d) Benjamin, R.; Travis,
B. R.; Ciaramitaro, B. P.; Borhan, B. Eur. J. Org. Chem. 2002, 3429. (e)
phenylboronic, and naphthaleneboronic acid failed to deliver Simon, J.; Salzbrunn, S.; Prakash, G. K. S.; Petasis, N. A.; Olah, G. A. J. Org.
the desired esters. Chem. 2001, 66, 633.