Organic Letters
Letter
a
Table 3. Suzuki−Miyaura Reactions of Aryl Fluorosulfates
ASSOCIATED CONTENT
* Supporting Information
■
S
Available full experimental details, spectroscopic data, and
1
copies of H and 13C NMR for compounds. This material is
f
entry
Ar1
Ar2
time (h)
yield (%)
1
2
3
4-MeO2SC6H4
4-EtOOCC6H4
4-O2NC6H4
2-MeOC6H4
4-MeOC6H4
4-NCC6H4
4-NCC6H4
4-NCC6H4
4-O2NC6H4
4-EtOOCC6H4
4-EtOOCC6H4
2-NCC6H4
2-MeOC6H4
2-Naph
Ph
Ph
Ph
Ph
Ph
2
2
2
6
6
2
2
2
2
2
2
10
6
2
3
3
6
6
2
2
2
93
99
96
94
90
93
94
91
93
93
99
71
87
94
99
94
93
95
59
75
70
AUTHOR INFORMATION
Corresponding Authors
■
b
4
b
5
Notes
6
4-MeOC6H4
4-FC6H4
7
8
4-F3CC6H4
4-MeOC6H4
4-OMeC6H4
2-MeC6H4
4-MeC6H4
4-F3CC6H4
Ph
The authors declare no competing financial interest.
9
10
11
12
ACKNOWLEDGMENTS
■
This work was supported by the China Basic Research Program
(973-2010CB833200/300), NSFC (21102167), Sci. & Tech.
Commission of Shanghai Municipality (12DZ1930902), and
Knowledge Innovation Program of the Chinese Academy of
Sciences.
b
13
14
c
15
2-Naph
4-MeOC6H4
4-MeOC6H4
4-FC6H4
c
16
1-Naph
d
17
1,4-C6H4
d
18
4,4′-(C6H4)2SO2
4-O2NC6H4
4-O2NC6H4
4-EtOOCC6H4
Ph
REFERENCES
■
e
19
Ph
(1) Rosen, B. M.; Quasdorf, K. W.; Wilson, D. A.; Zhang, N.;
Resmerita, A.-M.; Garg, N. K.; Percec, V. Chem. Rev. 2010, 111, 1346.
(2) Rappoport, Z. The Chemistry of Phenols; Wiley: New York, 2004.
(3) (a) Wang, C.; Ozaki, T.; Takita, R.; Uchiyama, M. Chem.Eur. J.
2012, 18, 3482. (b) Yu, D.-G.; Li, B.-J.; Shi, Z.-J. Acc. Chem. Res. 2010,
43, 1486. (c) Moser, R.; Nishikata, T.; Lipshutz, B. H. Org. Lett. 2009,
12, 28. (d) Kakiuchi, F.; Usui, M.; Ueno, S.; Chatani, N.; Murai, S. J.
Am. Chem. Soc. 2004, 126, 2706. (e) Dankwardt, J. W. Angew. Chem.,
Int. Ed. 2004, 43, 2428. (f) Boom, M. E.; Liou, S.-Y.; Ben-David, Y.;
Shimon, L. J. W.; Milstein, D. J. Am. Chem. Soc. 1998, 120, 6531.
(g) Nomura, N.; RajanBabu, T. V. Tetrahedron Lett.1997, 38, 1713.
(h) Wenkert, E.; Michelotti, E. L.; Swindell, C. S.; Tingoli, M. J. Org.
Chem. 1984, 49, 4894. (i) Wenkert, E.; Michelotti, E. L.; Swindell, C.
S. J. Am. Chem. Soc. 1979, 101, 2246.
e
20
4-MeOC6H4
4-MeOC6H4
e
21
a
General conditions: rt, aryl-OSO2F(1.0 mmol), arylboronic acid (1.5
mmol), Pd(OAc)2 (1 mol %), Et3N (3.0 mmol), H2O (3.0 mL), under
air. Pd(OAc)2 (5 mol %), Et3N (5.0 mmol). Pd(OAc)2 (1 mol %),
b
c
d
Et3N (5.0 mmol). Pd(OAc)2 (3 mol %), Et3N (10.0 mmol).
e
f
Potassium aryltrifluoroborate (1.5 mmol). Isolated yields.
Table 4. Other Types of Coupling Reactions Using OSO2F
d
entry
aryl-OSO2F
coupling partner
time (h)
yield (%)
a
1
4-O2NC6H4
methyl acrylate
phenyl acetylene
24
4
63
73
69
b
2
2-OHCC6H4
4-EtOOCC6H4
(4) Pedley, J. B.; Naylor, R. D.; Kirby, S. Thermochemical Data of
Organic Compounds; Springer: Dordrecht, 1986
c
3
20
a
4-Nitrophenyl fluorosulfate (2.0 mmol), methyl acrylate (4.0 mmol),
Pd(OAc)2 (2 mol %), dppp (3 mol %), Et3N (2.4 mmol), DMF (5
mL), in argon at 80 °C, 24 h. 2-Formylphenyl fluorosulfate (2.0
mmol), phenylacetylene (2.8 mmol), PdCl2(PPh3)2 (2 mol %), Et3N
(5) Scott, W. J.; Crisp, G. T.; Stille, J. K. J. Am. Chem. Soc. 1984, 106,
4630.
(6) So, C. M.; Kwong, F. Y. Chem. Soc. Rev. 2011, 40, 4963.
(7) Li, B.-J.; Yu, D.-G; Sun, C.-L.; Shi, Z.-J. Chem.Eur. J. 2011, 17,
1728.
b
c
(5.0 mmol), DMF (0.7 mL), in argon at 80 °C, 4 h. Ethyl 4-
[(fluorosulfonyl)oxy]benzoate (2.0 mmol), NiCl2(PPh3)2 (10 mol %),
Zn (3.4 mmol), Bu4NI (3.0 mmol), THF (2 mL), in argon at 70 °C,
(8) Roth, G. P.; Fuller, C. E. J. Org. Chem. 1991, 56, 3493.
(9) (a) Roth, G. P.; Thomas, J. A. Tetrahedron Lett. 1992, 33, 1959.
(b) McGuire, M. A.; Sorenson, E.; Owings, F. W.; Resnick, T. M.; Fox,
M.; Baine, N. H. J. Org. Chem. 1994, 59, 6683.
d
20 h. Isolated yields.
(10) (a) Cramer, R.; Coffman, D. J. Org. Chem. 1961, 26, 4164.
(b) Boudakian, M. M.; Hyde, G. A.; Kongpricha, S. J. Org. Chem. 1971,
36, 940. (c) Stang, P. J.; Hanack, M.; Subramanian, L. Synthesis 1982,
85.
(11) (a) Dong, J.; Sharpless, K. B.; Kwisnek, L.; Oakdale, J. S.; Fokin,
V. V. Angew. Chem., Int. Ed. 2014, 53, 9466. (b) Dong, J.; Sharpless, K.
B.; Kwisnek, L.; Oakdale, J. S.; Fokin, V. V. Angew. Chem. 2014, 126,
9620.
(12) Andersen, S. P. S.; Blake, D. R.; Rowland, F. S.; Hurley, M. D.;
Wallington, T. J. Environ. Sci. Technol. 2009, 43, 1067.
(13) Mondal, M.; Bora, U. Green Chem. 2012, 14, 1873.
(14) Liu, C.; Ni, Q.; Bao, F.; Qiu, J. Green Chem. 2011, 13, 1260.
(15) Del Zotto, A.; Amoroso, F.; Baratta, W.; Rigo, P. Eur. J. Org.
Chem. 2009, 110.
(16) (a) Maegawa, T.; Kitamura, Y.; Sako, S.; Udzu, T.; Sakurai, A.;
Tanaka, A.; Kobayashi, Y.; Endo, K.; Bora, U.; Kurita, T.; Kozaki, A.;
Monguchi, Y.; Sajiki, H. Chem.Eur. J. 2007, 13, 5937. (b) Kitamura,
Y.; Sako, S.; Udzu, T.; Tsutsui, A.; Maegawa, T.; Monguchi, Y.; Sajiki,
H. Chem. Commun. 2007, 5069.
Sonogashira (Table 4, entry 2), and nickel-catalyzed homo-
coupling reactions (Table 4, entry 3), following the literature
methods.25 All the reactions proceeded smoothly and afforded
satisfactory results as shown in Table 4.
In summary, we developed a simple, efficient procedure for
the Suzuki−Miyaura cross-coupling reaction in water under
mild conditions using aryl fluorosulfates, which were prepared
by a clean, cheap, synthetic method, as coupling partners.
Furthermore, the fluorosulfates were demonstrated to be
versatile alternatives to triflates and could be widely used in
organic synthesis. Further applications of this useful coupling
partner are under investigation in our laboratory.
C
Org. Lett. XXXX, XXX, XXX−XXX