Novel Z-selective head-to-head dimerization of terminal alkynes catalyzed by lanthanide half-metallocene complexes

Journal of the American Chemical Society

Volumn 125, Issue 5, 2003, Pages 1184-1185

  Nishiura, Masayoshi ^a   Hou, Zhaomin ^a   Wakatsuki, Yasuo ^a   Yamaki, Taeko ^a,b   Miyamoto, Takeshi ^b  

^a INST OF PHYS AND CHEMICAL RESEARCH   (Japan)

^b KITASATO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; LANTHANIDE;

ARTICLE; CATALYSIS; CATALYST; COMPLEX FORMATION; DIMERIZATION; GAS CHROMATOGRAPHY; MASS SPECTROMETRY; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; X RAY ANALYSIS;

EID: 0037419829     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja027595d     Document Type: Article

References (35)

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31. See the Supporting Information for details.
32. 3a.c-e
33. A small amount of THF (2 equiv per 11 or 12) was required to achieve the exclusive head-to-head -dimerization of phenylacetylene, because 11 or 12 is a THF-free complex, while 8 or 9 bears a THF ligand. This result is in agreement with the THF effect observed above.
34. YC = 23 Hz) for the μ-alkynide carbon, suggesting that the μ-alkynide-bridged dimeric structure in this type of complex is considerably strong. Addition of 2 equiv of 4-(n-pentyl)phenylacetylene to this solution at 80 °C afforded quantitatively the corresponding Z-dimerization product in 3 h, while the triplet for the α-alkynide carbon remained almost unchanged after the reaction.
35. Path a could be a sterically favored process, while path b might be electronically preferred especially when R is an alkyl or electron-donating group. In the presence of THF, A might be preferred to B because of crowdedness caused by the THF molecules (ligands) around the metal centers. Further studies are in progress to clarify the mechanism.