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Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Journal Name
COMMUNICATION
Synthesis of the copper(I) complex [1](OTf).
helpful discussion.
DOI: 10.1039/C9DT01882D
The synthesis of complex [1]OTf was performed similar to a
3
c
previously reported procedure. In a 100 mL-Schlenk-flask the
bi-triazolium salt (H2L)(OTf)2 (263 mg, 0.348 mmol, 1 equiv.)
and sodium acetate (74.2 mg, 0.904 mmol, 2.6 equiv.) were
Conflicts of interest
There are no conflicts to declare.
2 2
stirred in dry and degassed CH Cl for 5 h at 30 °C. Freshly
prepared copper(I) acetate (158 mg, 1.29 mmol, 3.7 equiv.)
was added.15 The suspension was stirred for 2 days at 30 °C.
The resulting red suspension was filtered under inert
atmosphere and the solvent was removed under reduced
pressure. Addition of dry and degassed THF (5 mL) yielded
microcrystalline precipitate after about half an hour. The
solvent was decanted and the remaining solid was washed
with dry, degassed THF twice. After drying under vacuum
complex [1]OTf was obtained as an off-white solid with 0.6
entities of THF per complex molecule (38 %, 109 mg, 0.133
mmol). Single crystals suitable for X-ray diffraction were
Notes and references
1
a) V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless,
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Christensen, M. Meldal, J. Org. Chem., 2002, 67, 3057. c) P.
Thirumurugan, D. Matosiuk, K. Jozwiak, Chem. Rev., 2013,
1
13, 4905. d) A. H. El-Sagheer, T. Brown, Chem. Soc. Rev.
010, 39, 1388. e) P. L. Golas, K. Matyjaszewski, Marrying,
2
Chem. Soc. Rev. 2010, 39, 1338. f) L. Liang, D. Astruc, Coord.
Chem. Rev., 2011, 255, 2933.
2
3
a) T. R. Chan, R. Hilgraf, K. B. Sharpless, V. V. Fokin, Org. Lett.,
2
004, 6, 2853. b) V. Hong, S. I. Presolski, C. Ma, M. G. Finn,
2 2
observed by crystallizing in dry and degassed CH Cl layered
with pentane.
Angew. Chem. Int. Ed., 2009, 48, 9879.
a) S. Díez-González, A. Correa, L. Cavallo, S. P. Nolan, Chem
Eur. J., 2006, 12, 7558. (b) S. Díez-González, S. P. Nolan,
Angew. Chem. Int. Ed., 2008, 120, 9013. c) R. Berg, J. Straub,
E. Schreiner, S. Mader, F. Rominger, B. F. Straub, Adv. Synth.
Catal., 2012, 354, 3445. d) S. Hohloch, B. Sarkar, L. Nauton, F.
Cisnetti, A. Gautier, Tetrahedron Lett., 2013, 54, 1808. e) L.
Jin, D. R. Tolentino, M. Melaimi, G. Bertrand, Sci. Adv., 2015,
1, e1500304. (f) S. Hohloch, L. Suntrup, B. Sarkar, Inorganic
Chemistry Frontiers, 2016, 3, 67. g) T. Nakamura, T.
Terashima, K. Ogata, S.-I. Fukuzawa, Org. Lett., 2011, 13,
1
H NMR (400 MHz, CD
methylene-H), 2.09 (s, 3H, acetate-H) ppm. C NMR (101
MHz, CD Cl ) δ(ppm) = 83.38 (Ccarbene), 149.79, 135.15, 132.07,
30.93, 130.49, 130.10, 129.69, 127.22, 125.85, 70.50, 68.31
THF), 31.17, 26.14 (THF), 22.63. Anal. Calcd. (%) for
Cu S ∙ 0.60 C O] C 49.6, H 3.61, N 10.09; Found
2 2
Cl ) δ(ppm) = 7.75–7.28 (m, 22H, aryl-H
1
3
+
2
2
1
(
[
C
32 25
H N
6
2
O F
5 3
4 8
H
C 49.21, H 3.627, N 9.747. ESI-MS: m/z: [M–OTf]+ Calcd.
39.063, Found 639.062.
6
6
20. h) M.-L. Teyssot, A. Chevry, M. Traïkia, M. El-Ghozzi, D.
Avignant, A. Gautier, Chem. Eur. J., 2009, 15, 6322. i) C.
Gaulier, A. Hospital, B. Legeret, A. F. Delmas, V. Aucagne, F.
Cisnetti, A. Gautier, Chem. Commun., 2012, 48, 4005. j) W.
Wang, J. Wu, C. Xia, F. Li, Green Chem., 2011, 13, 3440. k) Y.
D. Bidal, M. Lesieur, M. Melaimi, F. Nahra, D. B. Cordes, K. S.
Athukorala Arachchige, A. M. Z. Slawin, G. Bertrand, C. S. J.
Cazin, Adv.Synth. Catal., 2015, 357, 3155. l) A. L. Schöffler, A.
Makarem, F. Rominger, B. F. Straub, Beilstein J. Org. Chem.
2016, 12, 1566. For a non-NHC copper binuclear catalyst,
see: m) H.-B. Chen, N. Abeyrathna, Y. Liao, Tetrahedron Lett.,
Catalysis.
All steps were carried out under air. In a vial the azide (0.4
mmol, 1 equiv.), alkyne (0.4 mmol, 1.0 equiv.) and 1,4-
dimethoxybenzene (6.9 mg, 0.05 mmol, 0.25 equiv.) as an
internal standard were solved in CDCl (2 mL), which was
3
previously deactivated over basic aluminum oxide. A sample of
1
the solution was taken to get a H NMR control spectrum. A
volume of 0.6 mL of the stock (cazide = calkyne = 0.2 mol/L) was
added to the catalyst [1]OTf (0.0012 mmol, 1 mol%) in a vial.
After solution of the complex, the sample was directly
2
014, 55, 6575.
4
5
B. T. Worrell, J. A. Malik, V. V. Fokin, Science, 2013, 340, 457.
L. Jin, E. A. Romero, M. Melaimi, G. Bertrand, J. Am. Chem.
Soc., 2015, 137, 15696.
1
transferred into an NMR tube and H NMR spectra were taken
6
7
8
L. Suntrup, S. Hohloch, B. Sarkar, Chem. Eur. J., 2016, 22,
to monitor the reaction. All spectra were retreated by
ACDNMR software using a house build macro. This macro
integrates automatically the signals of the internal standard
1
8009.
Reactions in coordinating, protic solvent (ie: MeOH) are
inefficient.
(1,4-DMB) at 6.9 ppm and two signals from the triazole: the
a) F. Himo, T. Lovell, R. Hilgraf, V. V. Rostovtsev, L.
Noodleman, K. B. Sharpless, V. V. Fokin, J. Am. Chem. Soc.,
benzylic CH at 5.6 ppm and the CH OH at 3.75 ppm.
2
2
2
005, 127, 210-216. b) M. Ahlquist, V. V. Fokin,
Completions were calculated as the average of the two triazole
integrations based on the constant amount of internal
standard. As ACDNMR macro furnish a txt file for each
spectrum, all these files were compiled in a single txt file and
were include in an excel file for calculation.
Organometallics, 2007, 26, 4389.
9
1
a) ref 3e. b) G.-C. Kuang, P. M. Guha, W. S. Brotherton, J. T.
Simmons, L. A. Stankee, B. T. Nguyen, R. J. Clark, L. Zhu, J.
Am. Chem. Soc., 2011, 133, 13984. c) C. Nolte, P. Mayer, B. F.
Straub, Angew. Chem. Int. Ed. 2007, 46, 2101.
0 a) A. Kina, Y. Yasuhara, T. Nishimura, H. Iwamura, T. Hayashi,
Chem. Asian J., 2006, 1, 707. b) T. Rosner, J. Le Bars, A. Pfaltz,
D. G. Blackmond, J. Am. Chem. Soc., 2011, 123, 1848. c) A.
Kina, H. Iwamura, T. Hayashi, J. Am. Chem. Soc., 2006, 128,
Acknowledgment
This work was partly funded by DAAD/Campus France
under the Procope program (through funds from the
Bundesministerium für Bildung und Forschung “BMBF”) and
3
904.
1
1
1 A. Makarem, R. Berg, F. Rominger, B. F. straub, Angew.
Chem. Int. Ed. 2015, 54, 7431.
2 A large range of guess values converge identically (RMS =
-
3
1
.7.10 ).
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