C O M M U N I C A T I O N S
Table 2. Pd-Catalyzed Hiyama Cross-Coupling Reactions of
Arenesulfonate 1 with Arylsilane 2
Scheme 1
entry
R1/Ar
R2/R
yield (%)a
1
2
3
4
5
6
7
8
4-t-BuC6H4/4-MeC6H4 1a
4-PhC6H4/4-MeC6H4 1b
4-EtO2CC6H4/4-MeC6H4 1c
4-NCC6H4/4-MeC6H4 1d
R-naphthyl/4-MeC6H4 1e
R-naphthyl/C6H5 1f
ꢀ-naphthyl/4-MeC6H4 1g
3-morpholinylphenyl/
4-MeC6H4 1h
3-MeOC6H4/4-MeC6H4 1i
4-tert-pentylphenyl/
4-MeC6H4 1j
4-CF3C6H4/4-MeC6H4 1k
ꢀ-naphthyl/4-MeC6H4 1g
R-naphthyl/4-MeC6H4 1e
3-MeC6H4/4-MeC6H4 1l
3-morpholinylphenyl/
4-MeC6H4 1h
C6H5/Me 2a
C6H5/Me 2a
C6H5/Me 2a
C6H5/Me 2a
C6H5/Me 2a
C6H5/Me 2a
C6H5/Me 2a
C6H5/Me 2a
88 (3a)
67 (3b)
62 (3c)
72 (3d)
88 (3e)
94 (3e)
95 (3f)
97 (3g)
formation proceeds under mild conditions with good functional
group tolerance.
Acknowledgment. Financial support from National Natural
Science Foundation of China (20502004), and Shanghai Pujiang
Program is gratefully acknowledged. We also thank Dr. Jason Wong
(Roche R&D Center, China) for English review.
9
10
C6H5/Me 2a
C6H5/Et 2b
85 (3h)
81 (3i)
11
12
13
14
15
C6H5/Et 2b
C6H5/Et 2b
4-MeOC6H4/Me 2c
4-MeOC6H4/Me 2c
4-MeC6H4/Me 2d
81 (3j)
99 (3f)
81 (3k)
68 (3l)
81 (3m)
Supporting Information Available: Experimental procedures,
characterization data, copies of 1H and 13C NMR of compound 3. This
information is available free of charge via the Internet at http://
pubs.acs.org.
16
17
18
19
20
21
22
23
ꢀ-naphthyl/4-MeC6H4 1g
4-MeC6H4/Me 2d
4-MeC6H4/Me 2d
4-CF3C6H4/Me 2e
4-CF3C6H4/Me 2e
2-MeC6H4/Me 2f
C6H5/Me 2a
78 (3n)
63 (3o)
91 (3p)
85 (3q)
53 (3r)
30 (3s)
31 (3t)
trace
R-naphthyl/C6H5 1f
References
R-naphthyl/4-MeC6H4 1e
3-MeOC6H4/4-MeC6H4 1i
4-t-BuC6H4/4-MeC6H4 1a
2-MeC6H4/4-MeC6H4 1m
3-pyridinyl/4-MeC6H4 1n
ꢀ-naphthyl/4-MeC6H4 1g
(1) For selected examples, see: (a) Hiyama, T. In Metal-Catalyzed Cross-
Coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: New York,
1998; Chapter 10. (b) Hiyama, T. J. Organomet. Chem. 2002, 653, 58. (c)
Denmark, S. E.; Baird, J. D. Chem.sEur. J. 2006, 12, 4954. (d) Strotman,
N. A.; Sommer, S.; Fu, G. C. Angew. Chem., Int. Ed. 2007, 46, 3556. (e)
Ackermann, L.; Gschrei, C. J.; Althammer, A.; Riederer, M. Chem. Commun.
2006, 1419. (f) Wolf, C.; Lerebours, R. Org. Lett. 2004, 6, 1147.
(2) For some recent developments in Hiyama cross-coupling chemistry, see:
(a) Denmark, S. E.; Sweis, R. F. Acc. Chem. Res. 2002, 35, 835. (b) Itami,
K.; Nokami, T.; Yoshida, J.-i. J. Am. Chem. Soc. 2001, 123, 5600. and
references therein. (c) Lee, J.-Y.; Fu, G. J. Am. Chem. Soc. 2003, 125, 5616.
(d) Clarke, M. L. AdV. Synth. Catal. 2005, 347, 303. (e) Seganish, W. M.;
Handy, C. J.; DeShong, P. J. Org. Chem. 2005, 70, 8948. (f) Alacid, E.;
Na´jera, C. AdV. Synth. Catal. 2006, 348, 945. (g) Denmark, S. E.; Butler,
C. R. Org. Lett. 2006, 8, 63.
(3) Onak, T. Organoborane Chemistry; Academic Press: New York, 1975.
(4) For examples of Suzuki-Miyaura reactions, see: (a) Tang, Z.-Y.; Hu, Q.-S
J. Am. Chem. Soc. 2004, 126, 3058. (b) Nguyen, H. N.; Huang, X.; Buchwald,
S. L. J. Am. Chem. Soc. 2003, 125, 11818. (c) Percec, V.; Bae, J.-Y.; Hill,
D. H. J. Org. Chem. 1995, 60, 1060. (d) Kobayashi, Y.; Mizojiri, R.
Tetrahedron Lett. 1996, 37, 8531. (e) Zim, D.; Lando, V. R.; Dupont, J.;
Monteiro, A. L. Org. Lett. 2001, 3, 3049. (f) Lakshman, M. K.; Thomson,
P. F.; Nuqui, M. A.; Hilmer, J. H.; Sevova, N.; Boggess, B. Org. Lett. 2002,
4, 1479. (g) Huffman, M. A.; Yasuda, N. Synlett 1999, 471. (h) Percec, V.;
Golding, G. M.; Smidrkal, J.; Weichold, O. J. Org. Chem. 2004, 69, 3447.
(i) Baxter, J. M.; Steinhuebel, D.; Palucki, M.; Davies, I. W. Org. Lett. 2005,
7, 215. (j) Tang, Z. Y.; Hu, Q.-S. AdV. Synth. Catal. 2004, 346, 1635. (k)
Steinhuebel, D.; Baxter, J. M.; Palucki, M.; Davies, I. W. J. Org. Chem.
2005, 70, 10124. (l) Netherton, M. R.; Fu, G. C. Angew. Chem., Int. Ed.
2002, 41, 3910. (m) Zhang, L.; Meng, T.; Wu, J. J. Org. Chem. 2007, 72,
9346.
(5) For examples of Sonogashira coupling, see: (a) Fu, X.; Zhang, S.; Yin, J.;
Schumacher, D. P Tetrahedron Lett. 2002, 43, 6673. (b) Gelman, D.;
Buchwald, S. L. Angew. Chem. 2003, 42, 5993. Heck coupling: Fu, X.;
Zhang, S.; Yin, J.; McAllister, T. L.; Jiang, S. A.; Tann, C.-H.; Thiruven-
gadam, T. K.; Zhang, F. Tetrahedron Lett. 2002, 43, 573. Kumada
coupling: (c) Roy, A. H.; Hartwig, J. F. J. Am. Chem. Soc. 2003, 125, 8704.
(d) Limmert, M. E.; Roy, A. H.; Hartwig, J. F. J. Org. Chem. 2005, 70,
9364. (e) Ackermann, L.; Althammer, A. Org. Lett. 2006, 8, 3457. Iron-
catalyzed coupling of alkyl Grignard reagents with ArOTs: (f) Fu¨rstner, A.;
Leitner, A.; Mendez, M.; Krause, H. J. Am. Chem. Soc. 2002, 124, 13856.
Stille couplings: (g) Badone, D.; Cecchi, R.; Guzzi, U. J. Org. Chem. 1992,
57, 6321. (h) Nagatsugi, F.; Uemura, K.; Nakashima, S.; Minoru, M.; Sasaki,
S. Tetrahedron Lett. 1995, 36, 421. (I) Schio, L.; Chatreaux, F.; Klich, M
TetrahedronLett.2000,41,1543.Negishi-typereactionofarenesulfonates:Zhou,
J.; Fu, G. C. J. Am. Chem. Soc. 2003, 125, 12527.
(6) (a) Martin, R.; Buchwald, S. L. Acc. Chem. Res. 2008,ASAP, DOI: 10.1021/
ar800036s and references therein. (b) Anderson, K. W.; Ikawa, T.; Tundel,
R. E.; Buchwald, S. L. J. Am. Chem. Soc. 2006, 128, 10694. (c) Huang, X.;
Anderson, K. W.; Zim, D.; Jiang, L.; Klapars, A.; Buchwald, S. L. J. Am.
Chem. Soc. 2003, 125, 6653. (d) Buchwald, S. L. AdV. Synth. Catal. 2004,
346, 1599.
C6H5/Me 2a
2-thiophenyl/Et 2g
a Isolated yield based on arenesulfonate 1.
desired product was generated in high yield. Excellent yield was
also observed when morpholinyl- or methoxy-substituted tosylate
1c or 1d was utilized as a substrate (Table 2, entries 8-9). Similar
results were obtained when triethoxy(phenyl)silane 2b was used
as a replacement for 2a in reactions with aryl arenesulfonates 1
(Table 2, entries 10-12). For instance, almost quantitative yield
of product 3f was generated for reaction of ꢀ-naphthyl tosylate 1g
with 2b (Table 2, entry 12). With respect to other arylsilanes 2c-2e,
as expected both electron-rich and -poor arylsilanes are suitable
partners in this process and the desired products were isolated in
good yields (Table 2, entries 13-19). However, the yield was
diminished when the silane or tosylate bearing ortho-substitution
was employed under the same conditions (Table 2, entries 20-21).
3-Pyridinyl tosylate was also utilized as a substrate in the reaction
of silane 2a affording the desired product 3t in 31% yield (Table
2, entry 22). Only a trace amount of product was detected for
reaction of 2-thiophenyl(triethoxy) silane 2g with tosylate 1g (Table
2, entry 23).
Interestingly, when 4-chlorophenyl tosylate 1o was employed
in the reaction of arylsilane 2c under the standard conditions shown
in Table 2 (Scheme 1, eq 1), the tosyloxy group in compound 1o
was retained during the transformation and the product 1p was
afforded in 70% yield. From this reaction, it was found that an
aryl chloride is more active than an aryl tosylate under the same
conditions. Similar to tosylate 1b, compound 1p could be further
elaborated to furnish the triaryl compound. This condition was also
applied in the reaction of vinyl tosylate. For example, vinyl tosylate
4 reacted with trimethoxy(phenyl)silane 2a leading to the corre-
sponding product 5 in 80% yield (Scheme 1, eq 2).
In conclusion, we have developed the first example of achieving
Hiyama couplings of aryl arenesulfonates. The desired C-C bond
JA804672M
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J. AM. CHEM. SOC. VOL. 130, NO. 37, 2008 12251