10.1002/anie.201910060
Angewandte Chemie International Edition
Acknowledgements
We gratefully acknowledge RWTH Aachen University and the Eu-
ropean Research Council (ERC-637993) for financial support.
I.F.A. acknowledges the Alexander von Humboldt Foundation for
a fellowship.
Conflict of interest
The authors declare no conflict of interests.
Author Information
C. Fricke, G. J. Sherborne, I. Funes-Ardoiz, E. Senol, S. Guven,
Prof. Dr. F. Schoenebeck
Saturation
Institute of Organic Chemistry, RWTH Aachen University,
Landoltweg 1, 52074 Aachen (Germany).
E-mail: franziska.schoenebeck@rwth-aachen.de
Author Contributions
†C.F. and G.J.S. contributed equally.
Received: ((will be filled in by the editorial staff))
Published online on ((will be filled in by the editorial staff))
Keywords: chemoselectivity • catalysis • DFT • germanium
[1] Research and Markets, “Global nanotechnology market (by compo-
nent and applications), funding & investment, patent analysis and 27
companies profile & recent developments - forecast to 2024” (2018;
Figure 7. Computational study of nanoparticle catalyzed cross cou-
pling Free energy diagram in kcal mol-1, calculated at CPCM (DMF)
B3LYP-D3/Def2TZVPP//B3LYP-D3/Def2SVP.[33]
[2] S. Handa, Y. Wang, F. Gallou, B. H. Lipshutz, Science 2015, 349,
1087-1091.
Conclusions: We developed the chemoselective coupling of
aryl iodides (and diaryliodonium salts) with aryl germanes un-
der nanoparticle catalysis in the presence of C-Br, C-Cl, C-
BPin, C-BMIDA and additional functionality. The method is
characterized by operational simplicity, air-tolerance, robust-
ness and can be performed under low Pd-loadings. The aryl ger-
manes were shown to be highly stable. For example, pen-
tafluoroaryl germane tolerates strong acids or bases over ex-
tended times and elevated temperature, whereas the correspond-
ing boronic acid has a life-time of milliseconds only. As such,
highly challenging couplings can readily be performed with aryl
germanes, including those involving 2-pyridyl or polyfluoro-
aryl germanes. Mechanistic and computational data are pre-
sented which unambiguously demonstrate that while organo-
germanes are the least reactive functionality under Pd(0)/Pd(II)
homogeneous molecular catalysis as compared to established
coupling partners, they are the most reactive group under nano-
particle conditions. The origin of this privileged reactivity was
found to lie in the electron-richness of aryl germanes, which
preferentially react via an electrophilic-aromatic substitution
type mechanism and as such are preferentially activated by
more electrophilic nanoparticles. These features in turn allow to
position organogermanes as orthogonal coupling motif to the
currently established and omnipresent cross-coupling regimes,
and showcase truly distinguished reactivity of nanoparticles as
compared to homogeneous molecular metal catalysts.
[3] R. F. Service, Science 2018, 330, 314-315.
[4] Chen et al. Science 2018, 359, 679–684.
[5] C. Deraedt, D. Astruc, Acc. Chem. Res. 2014, 47 (2), 494–503.
[6] (a) D. B. Eremin, V. P. Ananikov, Coord. Chem. Rev. 2017, 346, 2-
19. (b) N. T. S. Phan, M. van der Sluys, C. W. Jones, Adv. Synth.
Catal. 2006, 348, 609-679.
[7] M. T. Reetz, J. G. de Vries, Chem. Commun. 2004, 1559-1563.
[8] M. T. Reetz, E. Westermann, Angew. Chem. Int. Ed. 2000, 39, 165-
168.
[9] C. E. Tucker, J. G. de Vries, Topics in Catalysis 2002, 19 (1), 111-
118.
[10] (a) Transition Metal-Catalyzed Couplings in Process Chemistry:
Case Studies From the Pharmaceutical Industry (Eds.: Magano, J.;
Dunetz, J. R.), Wiley, Hoboken, 2013; (b) New Trends in Cross-Cou-
pling: Theory and Applications (Ed.: Colacot, T.), RSC Catalysis Se-
ries, Cambridge, 2015.
[11] For examples of iterative cross-couplings through transmetalation:
(a) C. M. Crudden, C. Ziebenhaus, J. P. G. Rygus, K. Ghozati, P. J.
Unsworth, M. Nambo, S. Voth, M. Hutchinson, V. S. Laberge, Y.
Maekawa, D. Imao, Nat. Commun. 2016, 7, 11065; (b) J. Li, S. G.
Ballmer, E. P. Gillis, S. Fujii, M. J. Schmidt, A. M. E. Palazzolo, J.
W. Lehmann, G. F. Morehouse, M. D. Burke, Science 2015, 347,
1221.
[12] C. C. C. J. Seechurn, M. O. Kitching, T. J. Colacot, V. Snieckus,
Angew. Chem. Int. Ed. 2012, 51, 5062-5085.
[13] A. A. Thomas, S. E. Denmark, Science 2016, 352, 329-332.
[14] a) P. A. Cox, M. Reid, A. G. Leach, A. D. Campbell, E. J. Kin, G. C.
Lloyd-Jones, J. Am. Chem. Soc. 2017, 139, 13156-13165; b) A. J. J.
This article is protected by copyright. All rights reserved.