Journal
CHEMSUSCHEM
Volume 12, Issue 14, Pages 3363-3369Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cssc.201900784
Keywords
alkenes; alkynes; hydrogenation; nickel; stereoselectivity
Funding
- European Research Council (EU) [670986-NoNaCat, 339 786-NAT_CAT]
- state of Mecklenburg-Vorpommern
- University of Amsterdam
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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.
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