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COMMUNICATIONS
Palladium-Catalysed Dehydrogenative sp C H Bonds Functionalisation
10269–10310; h) P. Thansandote, M. Lautens, Chem.
Experimental Section
Eur. J. 2009, 15, 5874–5883; i) X. Chen, K. M. Engle,
D.-H. Wang, J.-Q. Yu, Angew. Chem. 2009, 121, 5196–
5217; Angew. Chem. Int. Ed. 2009, 48, 5094–5115; j) L.
Ackermann, R. Vicente, A. Kapdi, Angew. Chem. 2009,
121, 9976–10011; Angew. Chem. Int. Ed. 2009, 48,
9792–9826; k) J. Roger, A. L. Gottumukkala, H.
Doucet, ChemCatChem 2010, 2, 20–40; l) N. Kuhl,
M. N. Hopkinson, J. Wencel-Delord, F. Glorius, Angew.
Chem. 2012, 124, 10382–10401; Angew. Chem. Int. Ed.
General
All reactions were performed in Schlenck tubes under
argon. DMA analytical grade was not distilled before use.
Commercial aryl bromide derivatives and amines were used
without purification. 1H (300 or 400 MHz), 13C (75 or
100 MHz) spectra were recorded in CDCl3 solutions. Chemi-
cal shifts are reported in ppm relative to CDCl3 (1H: 7.26
and 13C: 77.0). Flash chromatography was performed on
silica gel (230–400 mesh).
2012, 51, 10236–10254.
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[2] For reviews on sp C H bond functionalisation: a) R.
Giri, B.-F. Shi, K. M. Engle, N. Maugel, J.-Q. Yu,
Chem. Soc. Rev. 2009, 38, 3242–3272; b) F. Bellina, R.
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Chem. Soc. Rev. 2011, 40, 4902–4911; d) H. Li, B.-J. Li,
Z.-J. Shi, Catal. Sci. Technol. 2011, 1, 191–206.
Synthesis of 1a–1g, 3a–3g, 5a–5g, 7a–7g and 9a, 9b
A mixture of the 2-bromobenzenesulfonyl chloride deriva-
tive (2 mmol) and triethylamine (6 mmol) in CH2Cl2
(10 mL) was treated with the appropriate secondary amine
(2.2 mmol) in a dropwise fashion at 08C. Stirring was contin-
ued for 12 h and the reaction mixture was gradually warmed
to room temperature. The solvent was removed under re-
duced pressure and CH2Cl2 (20 mL) and H2O (20 mL) were
added. The resultant aqueous layer was further extracted
with CH2Cl2 (2ꢂ20 mL) and the combined CH2Cl2 extracts
were dried over MgSO4. Filtration followed by solvent re-
moval under vacuum afforded the crude product, which was
purified by flash column chromatography (pentane:diethyl
ether; 4:1) affording the product.
[3] a) O. Baudoin, A. Herrbach, F. Guꢀritte, Angew.
Chem. 2003, 115, 5914–5918; Angew. Chem. Int. Ed.
2003, 42, 5736–5740; b) J. Hitce, O. Baudoin, Adv.
Synth. Catal. 2007, 349, 2054–2060; c) J. Hitce, P. Re-
tailleau, O. Baudoin, Chem. Eur. J. 2007, 13, 792–799;
d) N. Martin, C. Pierre, M. Davi, R. Jazzar, O. Baudoin,
Chem. Eur. J. 2012, 18, 4480–4484; e) E. Motti, M. Cat-
ellani, Adv. Synth. Catal. 2008, 350, 565–569.
[4] For examples of formation of enamines from alkyla-
mines using cobalt, iridium, platinum or iron catalyst,
see: a) X. Zhang, A. Fried, S. Knapp, A. S. Goldman,
Chem. Commun. 2003, 2060–2061; b) A. D. Bolig, M.
Brookhart, J. Am. Chem. Soc. 2007, 129, 14544–14545;
c) X.-F. Xia, X.-Z. Shu, K.-G. Ji, Y.-F. Yang, A. Shau-
kat, X.-Y. Liu, Y.-M. Liang, J. Org. Chem. 2010, 75,
2893–2902; d) N. Takasu, K. Oisaki, M. Kanai, Org.
Lett. 2013, 15, 1918–1921. For sp3 functionalisation of
alkylamines with Ru and Ir catalysts, see also: e) B.
Sundararaju, Z. Tang, M. Achard, G. V. M. Sharma, L.
Toupet, C. Bruneau, Adv. Synth. Catal. 2010, 352,
3141–3146; f) B. Sundararaju, M. Achard, G. V. M.
Sharma, C. Bruneau, J. Am. Chem. Soc. 2011, 133,
10340–10343; g) X.-F. Xia, X.-Z. Shu, K.-G. Ji, A.
Shaukat, X.-Y. Liu, Y.-M. Liang, J. Org. Chem. 2011,
76, 342–345; h) K. Yuan, F. Jiang, Z. Sahli, M. Achard,
T. Roisnel, C. Bruneau, Angew. Chem. 2012, 124, 9006–
9010; Angew. Chem. Int. Ed. 2012, 51, 8876–8880; i) T.
Boudiar, Z. Sahli, B. Sundararaju, M. Achard, Z. Ka-
bouche, H. Doucet, C. Bruneau, J. Org. Chem. 2012,
77, 3674–3678; j) A. Millet, P. Larini, E. Clot, O. Bau-
doin, Chem. Sci. 2013, 4, 2241–2247.
General Procedure for the Synthesis of 2a–2g, 4a–4g,
6a–6g, 8a–8g, and 10a, 10b
A dry Schlenk tube was charged with 2-bromoarylsulfon-
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
dissolved in DMA (0.5 mL) was quickly added to the
Schlenk tube with a flow of argon, then DMA (1.5 mL) was
added. The Schlenk tube was closed and the reaction mix-
ture stirred at room temperature for 15 min. After heating
at 1508C for 16 h, and cooling, the solvent was removed
under vacuum, and the residue purified by flash chromatog-
raphy (diethyl ether:pentane).
Acknowledgements
This research was supported by a CEFIPRA fellowship. We
thank the CNRS for providing financial support.
[5] R. Giri, N. Maugel, B. M. Foxman, J.-Q. Yu, Organo-
metallics 2008, 27, 1667–1670.
[6] a) Y. Izawa, D. Pun, S. S. Stahl, Science 2011, 333, 209–
213; b) Y. Moon, D. Kwon, S. Hong, Angew. Chem.
2012, 124, 11495–11498; Angew. Chem. Int. Ed. 2012,
51, 11333–11336.
[7] J. Zhou, G. Wu, M. Zhang, X. Jie, W. Su, Chem. Eur. J.
2012, 18, 8032–8036.
[8] a) D. K. Rayabarapu, A. Zhou, K. O. Jeon, T. Samara-
koon, A. Rolfe, H. Siddiqui, P. R. Hanson, Tetrahedron
2009, 65, 3180–3188; b) S. Rousseaux, S. I. Gorelesky,
B. K. W. Chung, K. Fagnou, J. Am. Chem. Soc. 2010,
132, 10692–10705.
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