10.1002/chem.201803252
Chemistry - A European Journal
COMMUNICATION
[Au]
R
N
N3
[3]
[4]
[5]
J.-P. Zhang, Y.-B. Zhang, J.-B. Lin, X.-M. Chen, Chem. Rev. 2012, 112,
1001.
R
N
H
N
H
N2
HN3
C
+
TMSN3 MeOH
OR
[M]
K. Škoch, I. Císařová, J. Schulz, U. Siemeling, P. Štěpnička, Dalton
Trans. 2017, 46, 10339.
N
N N
R
[Au]
R
N
H
H
N
+
HN3
TMSOMe
N
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C
N
[Au]
N
NH
R
NH2
N
N
RNC
[Au]
R
HN
N
N
C
N
[Au]
[M]
N
[Au]
[M]
RNC
R
NH2
RNHC
N
N
N
6
N
5
[6]
[7]
M. Jafarzadeh, Synlett 2007, 2144.
Scheme 6. Plausible reaction mechanism showing the two interconnected
processes. Note: [M] = [Au] for Au-mediated transformation or void for a
possible spontaneous process suggested by other reactivity studies.
M. Gaydou, A. M. Echavarren, Angew. Chem. 2013, 125, 13710;
Angew. Chem. Int. Ed. 2013, 52, 13468.
[8]
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see: V. P. Boyarskiy, N. A. Bokach, K. V. Luzyanin, V. Y. Kukushkin,
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In conclusion, we describe the highly efficient (only 0.1
mol.% Au catalyst is required) and selective catalytic conversion
of isocyanides into cyanamides[18] or 1-substituted 1H-tetrazol-5-
amines, which is easily and reliably controlled by changing the
amount of the HN3 source. Furthermore, the reactions are widely
applicable and functional group-tolerant, thereby providing
safe[19] and nearly unlimited access to 1-substituted 1H-tetrazol-
5-amines, which are rapidly emerging as promising compounds
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[13] Although the latter transformation corresponds to an established route
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Acknowledgements
This work was funded by the Czech Science Foundation (project
no. 17-02495S).
Conflict of interests
[15] Some cyanamides could not be isolated due to their low stability.
[16] O. Tsuge, S. Urano, K. Oe, J. Org. Chem. 1980, 45, 5130.
[17] F. Tordini, A. Bencini, M. Bruschi, L. De Gioia, G. Zampella, P. Fantucci,
J. Phys. Chem. A 2003, 107, 1188.
The authors declare no conflict of interest.
Keywords: gold • cycloaddition • homogeneous catalysis •
[18] For an overview of the chemistry of cyanamides, see: a) M.-H. Larraufie,
G. Maestri, M. Malacria, C. Ollivier, L. Fensterbank, E. Lacôte,
Synthesis 1992, 1279; b) N. A. Bokach, V. Y. Kukushkin, Coord. Chem.
Rev. 2013, 257, 2293.
isocyanides • tetrazoles
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