Angewandte Chemie International Edition
10.1002/anie.201812577
COMMUNICATION
substituted, giving the product (3u) in 70% yield. Moreover, the
TIPS-substituted ethynylbenziodoxole reacted smoothly with
cyclopropenes bearing either alkyl or aryl groups, generating the
corresponding products (3s, 3t, 3x) in 64-80% yields. With only
one acceptor group on the cyclopropane, an uselective
decomposition was observed.
[5]
E. O. Asomoza-Solı´s, J. Rojas-Ocampo, R. A. Toscano, S. Porcel Chem.
Commun. 2016, 52, 7295.
[
6]
a) G. Zhang, Y. Peng, L. Cui, L. Zhang, Angew. Chem. Int. Ed. 2009, 48,
3112; Angew. Chem. 2009, 121, 3158; b) W. E. Brenzovich, D. Benitez,
A. D. Lackner, H. P. Shunatona, E. Tkatchouk, W. A. Goddard, F. D.
Toste, Angew. Chem. Int. Ed. 2010, 49, 5519; Angew. Chem. 2010, 122,
5651; c) T. De Haro, C. Nevado, J. Am. Chem. Soc. 2010, 132, 1512; d)
In summary, we have developed a new strategy for bimetallic
catalysis involving a Au(I)/Au(III) cycle, which provides a novel
way for the functionalization of cyclopropenes. The available
mechanistic data are consistent with the proposed oxidative
catalytic cycle involving an alkynyl Au(III) complex formed by the
L. T. Ball, G. C. Lloyd-Jones, C. A. Russell, Science 2012, 337, 1644; e)
S. Kramer, Chem. Eur. J. 2016, 22, 15584; f) L. Huang, M. Rudolph,
F.Rominger, A. S. K. Hashmi, Angew. Chem. Int. Ed. 2016, 55, 4808;
Angew. Chem. 2016, 128, 4888, g) A. Zeineddine, L. Estévez, S. Mallet-
Ladeira, K. Miqueu, A. Amgoune, D. Bourissou, Nat. Commun. 2017, 8,
565.
oxidative addition of the hypervalent iodine reagent onto
[
7]
8]
a) W. J. Wolf, M. S. Winston, F. D. Toste, Nat. Chem. 2014, 6, 159; b) J.
Guenther, S. Mallet-Ladeira, L. Estevez, K. Miqueu, A. Amgoune, D.
Bourissou, J. Am. Chem. Soc. 2014, 136, 1778; c) L. Huang, F.
Rominger, M. Rudolpha, A. S. K. Hashmi, Chem. Commun. 2016, 52,
64358; d) A. Tlahuext-Aca, M. N. Hopkinson, C. G. Daniliuc, F. Glorius,
Chem. Eur. J. 2016, 22, 11587.
+
(
Phen)Au+. The proposed active catalyst (Phen)Au was
synthesized and by comparison of the reaction rates to different
precatalyst, its role as actual active catalyst was demonstrated.
The potential alkynyl gold(III) intermediate was isolated by the
+
stoichiometric reaction of (Phen)Au with ethynylbenziodoxole. Its
[
a) J. P. Brand, J. Charpentier, J. Waser, Angew. Chem. Int. Ed. 2009, 48,
role as real intermediate was demonstrated by the alkynylation of
a cyclopropene in a stoichiometric experiment. The essential role
9346; Angew. Chem. 2009, 121, 9510; b) J. P. Brand, J. Waser, Angew.
Chem. Int., Ed. 2010, 49, 7304; Angew. Chem. 2010, 122, 7462; c) Y. Li,
J. P. Brand, J. Waser, Angew. Chem. Int. Ed. 2013, 52, 6743; Angew.
Chem. 2013, 125, 6875; d) H. Peng, Y. Xi, N. Ronaghi, B. Dong, N. G.
Akhmedov, X. Shi, J. Am. Chem. Soc. 2014, 136, 13174; e) Y. Ma, S.
Zhang, S. Yang, F. Song, J. You, Angew. Chem. Int. Ed. 2014, 53, 7870;
f) R. Cai, M. Lu, E. Y. Aguilera, Y. Xi, N. G. Akhmedov, J. L. Petersen, H.
Chen, X. Shi, Angew. Chem. Int. Ed. 2015, 54, 8772; Angew. Chem.
2
of AgNTf , together with the H/D exchange experiments, suggests
that the silver salt instead of gold is responsible for the C−H
cleavage of the cyclopropenes.
Acknowledgements
2015, 127, 8896; g) X. Li, X. Xie, N. Sun, Y. Liu, Angew. Chem. Int. Ed.
017, 56, 6994; Angew. Chem. 2017, 129, 7098; h) H. Ghari, Y. Li, R.
2
Yang, Y. Y.; Hu, L. and Zhang L. are grateful for a Ph.D. fellowship
from the China Scholarship Council (CSC).
Roohzadeh, P. Caramenti, J. Waser, A. Ariafard, Dalton Trans. 2017, 46,
12257; i) S. Banerjee, N. T. Patil, Chem. Commun. 2017, 53, 7937.
R. Kumar, C. Nevado, Angew. Chem. Int. Ed. 2017, 56, 1994; Angew.
Chem. 2017, 129, 2024.
[
9]
Keywords: bimetallic catalysis • isolated gold intermediates •
[
[
[
10] X. C. Cambeiro, N. Ahlsten, I. Larrosa, J. Am. Chem. Soc. 2015, 137,
5636.
11] a) S. Chuprakov, M. Rubin, V. Gevorgyan, J. Am. Chem. Soc. 2005, 127,
714; c) Z.-B. Zhu, Y. Wei, M. Shi, Chem. Soc. Rev. 2010, 40, 5534.
cross-coupling • C-H activation • cyclopropenes
1
[
1]
a) M. M. Hansmann, A. S. K. Hashmi, M. Lautens, Org. Lett. 2013, 15,
3
3226; b) M. N. Hopkinson, A. Tlahuext-Aca, F. Glorius, Acc. Chem. Res.
2016, 49, 2261; c) J. M. Alonso, M. P. Munoz, Angew. Chem. Int. Ed.
2018, 57, 4742; Angew.Chem. 2018, 130, 4832.
12] a) C. Song, L. Ju, M. Wang, P. Liu, Y. Zhang, J. Wang, Z. Xu, Chem. Eur.
J. 2013, 19, 3584; b) X. Wang, A. Lerchen, C. G. Daniliuc, F. Glorius,
Angew. Chem., Int. Ed. 2018, 57, 1712; Angew. Chem. 2018, 130, 1728.
13] M. J. Harper, C. J. Arthur, J. Crosby, E. J. Emmett, R. L. Falconer, A. J.
Fensham-Smith, P. J. Gates, T. Leman, J. E. McGrady, J. F. Bower, C.
A. Russell, J. Am. Chem. Soc. 2018, 140, 4440.
[
2]
3]
M. M. Lorion, K. Maindan, A. R. Kapdi, L. Ackermann, Chem. Soc. Rev.
017, 46, 7399.
a) Y. Shi, K. E. Roth, S. D. Ramgren, S. A. Blum, J. Am. Chem. Soc.
[
2
[
2009, 131, 18022; b) D. Weber, M. R. Gagné, Chem. Commun. 2011,
[
14] S. Komiya, T. A. Albright, R. Hoffmann, J. K. Kochi, J. Am. Chem. Soc.
47, 5172; c) A. S. K. Hashmi, C. Lothschütz, R. Döpp, M. Ackermann, J.
1976, 98, 7255.
De Buck Becker, M. Rudolph, C. Scholz, F. Rominger, Adv. Synth. Catal.
[
15] a) S. Y. Lee, J. F. Hartwig, J. Am. Chem. Soc. 2016, 138, 15278; b) D.
Whitaker, J. Bures, I. Larrosa, J. Am. Chem. Soc. 2016, 138, 8384; c) M.
D. Lotz, N. M. Camasso, A. J. Canty, M. S. Sanford, Organometallics
2012, 354, 133; d) M. Al-Amin, K. E. Roth, S. A. Blum, ACS Catal. 2014,
4, 622; e) M. Al-Amin, J. S. Johnson, S. A. Blum, Organometallics 2014,
33, 5448.
2
017, 36, 165.
16] A. Fattahi, R. E. McCarthy, M. R. Ahmad, S. R. Kass, J. Am. Chem. Soc.
003, 125, 11746.
[4]
P. Garcia-Dominguez, C. Nevado, J. Am. Chem. Soc. 2016, 138, 3266.
[
2
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