L. Chen, H. Lang, L. Fang, J. Yu, L. Wang
SHORT COMMUNICATION
Organomet. Chem. 1999, 576, 147–168; c) S. Kotha, K. Lahiri,
D. Kashinath, Tetrahedron 2002, 58, 9633–9695; d) N. Mi-
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Carpita, R. Rossi, Synthesis 2004, 15, 2419–2440; f) R. Martin,
S. L. Buchwald, Acc. Chem. Res. 2008, 41, 1461–1473.
organic synthesis. As the nickel-catalyzed desulfitative
cross-coupling reaction with arylboronic acids is disclosed
for the first time, studies on other nickel-catalyzed desulfit-
ative reactions are currently underway in our laboratory.
[
5] V. Percec, J.-Y. Bae, D. H. Hill, J. Org. Chem. 1995, 60, 1060–
1065.
Experimental Section
[6] F.-S. Han, Chem. Soc. Rev. 2013, 42, 5270–5298.
[
7] For Ni-catalyzed Suzuki aryl–aryl couplings of aryl chlorides,
see: a) S. Saito, M. Sakai, N. Miyaura, Tetrahedron Lett. 1996,
37, 2993–2996; b) A. F. Indolese, Tetrahedron Lett. 1997, 38,
3513–3516; c) S. Saito, S. Ohtani, N. Miyaura, J. Org. Chem.
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Yang, Tetrahedron Lett. 2007, 48, 2427–2430; h) Y.-L. Zhao, Y.
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beater, S. M. Resouly, Tetrahedron 1999, 55, 11889–11894; j) D.
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General Procedure for the Desulfitative Suzuki–Miyaura Cross-Cou-
pling Reactions of N,N-Disulfonylmethylamines and Arylboronic
Acids: A 25 mL Schlenk tube equipped with a magnetic bar was
charged with NiCl
onylmethylamine (0.25 mmol), the arylboronic acid (0.63 mmol),
and anhydrous K PO (1.00 mmol, 212.3 mg). The tube was then
evacuated (3ϫ 10 min) under vacuum and backfilled with N . Dry
2
(dppp) (0.0125 mmol, 6.8 mg), the N,N-disulf-
3
4
2
dioxane (3.0 mL) was injected by syringe, and the mixture was
stirred at 110 °C until the N,N-disulfonylmethylamine had disap-
peared, as monitored by TLC. The mixture was then poured into
water (20 mL) and extracted with CH
bined organic layer was dried with anhydrous Na
concentrated to dryness. The crude material was purified by flash
2
Cl
2
(3ϫ20 mL). The com-
2
SO , filtered, and
4
[8] For recent reports on Ni-catalyzed Suzuki reactions, by using
aryl carboxylates, see: a) B.-T. Guan, Y. Wang, B.-J. Li, D.-G.
Yu, Z.-J. Shi, J. Am. Chem. Soc. 2008, 130, 14468–14470; b)
K. W. Quasdorf, X. Tian, N. K. Garg, J. Am. Chem. Soc. 2008,
chromatography (silica gel, hexane/ethyl acetate or hexane/CH
to give the desired cross-coupled products.
2 2
Cl )
General Procedure for the Synthesis of N,N-Disulfonylmethylamines:
The sulfonyl chloride (1 mmol) was added at room temperature to
a solution of methylamine (1.1 mol, 25% aq. soln) in distilled water
130, 14422–14423; by using aryl carbamates: c) K. W. Quas-
dorf, M. Riener, K. V. Petrova, N. K. Garg, J. Am. Chem. Soc.
2009, 131, 17748–17749; d) A. Antoft-Finch, T. Blackburn, V.
Snieckus, J. Am. Chem. Soc. 2009, 131, 17750–17752; e) L. Xu,
B.-J. Li, Z.-H. Wu, X.-Y. Lu, B.-T. Guan, B.-Q. Wang, K.-Q.
Zhao, Z.-J. Shi, Org. Lett. 2010, 12, 884–887; by using aryl
methyl ether: f) M. Tobisu, T. Shimasaki, N. Chatani, Angew.
Chem. Int. Ed. 2008, 47, 4866–4869; Angew. Chem. 2008, 120,
(2 mL), and vigorous stirring was continued until the reaction was
complete (monitored by TLC). Sometimes, NaOH (1 mmol) was
added to promote the conversion of the sulfonyl chloride. The mix-
ture was then extracted with CH
bined organic layer was dried with anhydrous Na
concentrated to dryness. The crude residue was then dissolved in
dry CH Cl (50 mL), and another portion of the sulfonyl chloride
1.1 mmol) and Et N (3 mmol) was added with stirring. The mix-
2
Cl
2
(3ϫ 30 mL), and the com-
2
SO , filtered, and
4
4944–4947.
[
9] For recent reports on Ni-catalyzed Suzuki reactions by using
aryl sulfonates, see: a) D. Zim, V. R. Lando, J. Dupont, A. L.
Monteiro, Org. Lett. 2001, 3, 3049–3051; b) Z.-Y. Tang, Q.-S.
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Kuroda, K. Inamoto, K. Hiroya, T. Doi, Eur. J. Org. Chem.
2
2
(
3
ture was then slowly heated to a gentle reflux. Upon completion
of the reaction (monitored by TLC), water (ca. 50 mL) was added,
and the mixture was extracted with CH
bined organic layer was dried with anhydrous Na
concentrated to dryness again. The crude material was purified by
column chromatography (cyclohexane/dichloromethane, 5:1 to
2
Cl
2
(3ϫ 30 mL). The com-
SO , filtered, and
2
4
2
009, 2251–2261; f) G. A. Molander, F. Beaumard, Org. Lett.
2
010, 12, 4022–4025; g) X.-H. Fan, L.-M. Yang, Eur. J. Org.
1:1).
Chem. 2010, 2457–2460; h) T. Tu, H. Mao, C. Herbert, M. Xu,
K. H. Dötz, Chem. Commun. 2010, 46, 7796–7798; i) H. Gao,
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353, 309–314; j) P. Leowanawat, N. Zhang, A.-M. Resmerita,
B. M. Rosen, V. Percec, J. Org. Chem. 2011, 76, 9946–9955; k)
G.-J. Chen, F.-S. Han, Eur. J. Org. Chem. 2012, 3575–3579.
Supporting Information (see footnote on the first page of this arti-
1
cle): Experimental details and copies of the H NMR and
13
C NMR spectra.
Acknowledgments
[10] For heterogeneous Ni-catalyzed Suzuki reactions, see: a) B. H.
Lipshutz, J. A. Sclafani, P. A. Blomgren, Tetrahedron 2000, 56,
2
139–2144; b) B. H. Lipshutz, T. Butler, E. Swift, Org. Lett.
The work was supported by the National Nature Science Founda-
tion of China (NSFC) (grant numbers 21272069 and 21202186)
and by the Chinese Academy of Sciences, Shanghai Institute of
Organic Chemistry, Key Laboratory of Organofluorine Chemistry
2
008, 10, 697–700; c) S.-Z. Ge, J. F. Hartwig, Angew. Chem.
Int. Ed. 2012, 51, 12837–12841; Angew. Chem. 2012, 124,
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3009–13013.
11] Y.-L. Zhao, Y. Li, Y. Li, L.-X. Gao, F.-S. Han, Chem. Eur. J.
010, 16, 4991–4994.
12] G.-J. Chen, J. Huang, L.-X. Gao, F.-S. Han, Chem. Eur. J. 2011,
7, 4038–4042.
[
[
(Fundamental Research Funds for the Central Universities).
2
1
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