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Nickel-Catalyzed Stereodivergent Synthesis of E- and Z-Alkenes by Hydrogenation of Alkynes
K. Murugesan, , P.R. Linnebank, A. Spannenberg, J.N.H. Reek, R.V. Jagadeesh, M. Beller
Published in Wiley-VCH Verlag
PMID: 30977957
Volume: 12
Issue: 14
Pages: 3363 - 3369
A convenient protocol for stereodivergent hydrogenation of alkynes to E- and Z-alkenes by using nickel catalysts was developed. Simple Ni(NO3)2⋅6 H2O as a catalyst precursor formed active nanoparticles, which were effective for the semihydrogenation of several alkynes with high selectivity for the Z-alkene (Z/E>99:1). Upon addition of specific multidentate ligands (triphos, tetraphos), the resulting molecular catalysts were highly selective for the E-alkene products (E/Z>99:1). Mechanistic studies revealed that the Z-alkene-selective catalyst was heterogeneous whereas the E-alkene-selective catalyst was homogeneous. In the latter case, the alkyne was first hydrogenated to a Z-alkene, which was subsequently isomerized to the E-alkene. This proposal was supported by density functional theory calculations. This synthetic methodology was shown to be generally applicable in >40 examples and scalable to multigram-scale experiments. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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PublisherData powered by TypesetWiley-VCH Verlag