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ChemComm
Team Program (No. 2009010058) and The National High-tech
R&D Program of China (863 Program, No. 2013AA092903) for
financial support.
Notes and references
40 a Institute of Drug Synthesis and Pharmaceutical Process, School of
Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou, 510006
(P. R. China). Fax: (+86)-20-39943048; E-mail: lugui@mail.sysu.edu.cn
b Institute of Human Virology, Sun Yat-sen University, Guangzhou,
510080 (P. R. China)
45 † Electronic Supplementary Information (ESI) available: [Experimental
procedures, characterization data, 1H and 13C NMR spectra]. See DOI:
10.1039/b000000x/
Scheme 3 a) Hiyama reaction of N’-tosyl phenylhydrazine with arylsilane. b)
Cross-coupling of N’-tosyl phenylhydrazine with aryl iodide
also afforded 4-methoxybiphenyl 3a in 100% conversion
(Scheme 4a). In the absence of any palladium catalyst and aryl
boronic acid, the in situ generated diazene 1a’ would presumably
dissociate to give C6H5N2· radical and TolSO2· radical, the
former may release nitrogen and form diphenyl compound, while
the latter yields the thiosulfonate (Scheme 4b).10a
5
1
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10
Scheme 4 Control experiments. PMP = p-methoxyphenyl, Ts = tolylsulfinate,
Tol = tolyl.
3
4
Based on these experiments, a possible mechanism for this
hydrazine Suzuki reaction has been proposed (Figure 1). N’-tosyl
5
15 arylhydrazine A was dehydrogenated in the presence of base to
provide the diazene B, which was in equilibrium with the
corresponding diazonium ion.10 Then an oxidative addition of
diazonium ion to Pd-catalyst gave the organopalladium
intermediate C, which promoted the transmetallation of the
20 arylboronic acid to form the diaryl-palladium species D. Finally a
reductive elimination of D afforded the corresponding biaryl
product E and regenerated the Pd-catalyst.
6
7
8
Figure 1 Proposed mechanism for the Suzuki cross-coupling of N'-tosyl
25 arylhydrazines with arylboronic acid
N’-tosyl arylhydrazines were prepared from the corresponding
arylhydrazine by tosylation with TsCl. See: N. Zhao, Y. Li, Y.
Wang and J. Wang, J. Sulfur Chem., 2006, 27, 427.
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2007, 46, 3556; (c) L. Zhang and J. Wu, J. Am. Chem. Soc., 2008,
130, 12250.
In summary, we have described a new procedure for the
preparation of biaryl compounds by Pd-catalyzed Suzuki cross-
coupling between N’-tosyl arylhydrazine and various
organoboron reagents. Notably, N’-tosyl arylhydrazine as a
30 readily available and stable electrophile demonstrated its
9
generality in
a number of coupling reactions. This new
10 (a) J. L. Kice and R. S. Gabrielsen, J. Org. Chem., 1970, 35, 1004;
(b) C. D. Ritchie, J. D. Saltiel and E. S. Lewis, J. Am. Chem. Soc.,
1961, 83, 4601.
methodology can be used as a complement for the classical
Suzuki cross-coupling reaction.
We thank the National Natural Science Foundation of China
35 (No. 20772161, 21262008), Guangdong Innovative Research