120368-06-1Relevant articles and documents
Origins of initiation rate differences in ruthenium olefin metathesis catalysts containing chelating benzylidenes
Engle, Keary M.,Lu, Gang,Luo, Shao-Xiong,Henling, Lawrence M.,Takase, Michael K.,Liu, Peng,Houk,Grubbs, Robert H.
supporting information, p. 5782 - 5792 (2015/05/20)
A series of second-generation ruthenium olefin metathesis catalysts was investigated using a combination of reaction kinetics, X-ray crystallography, NMR spectroscopy, and DFT calculations in order to determine the relationship between the structure of the chelating o-alkoxybenzylidene and the observed initiation rate. Included in this series were previously reported catalysts containing a variety of benzylidene modifications as well as four new catalysts containing cyclopropoxy, neopentyloxy, 1-adamantyloxy, and 2-adamantyloxy groups. The initiation rates of this series of catalysts were determined using a UV/vis assay. All four new catalysts were observed to be faster-initiating than the corresponding isopropoxy control, and the 2-adamantyloxy catalyst was found to be among the fastest-initiating Hoveyda-type catalysts reported to date. Analysis of the X-ray crystal structures and computed energy-minimized structures of these catalysts revealed no correlation between the Ru-O bond length and Ru-O bond strength. On the other hand, the initiation rate was found to correlate strongly with the computed Ru-O bond strength. This latter finding enables both the rationalization and prediction of catalyst initiation through the calculation of a single thermodynamic parameter in which no assumptions about the mechanism of the initiation step are made.
STEREOELECTRONIC STABILIZATION IN NON-CHAIR CONFORMATIONS OF SUBSTITUTED-2,3-DIHYDRO-1,4-BENZODIOXEPINS
Lachapelle, Alain,St-Jacques, Maurice
, p. 5033 - 5044 (2007/10/02)
2,3-Dihydro-1,4-benzodioxepin (5) and its 3-substituted derivatives 6-9 have been studied by (13)C and (1)H dynamic NMR in two solvent systems of different polarity.The aromatic signals were found to be quite sensitive to the nature of the seven-membered cyclic geometries and were used as "conformational probes".The results show that the chair (C) conformation is the only form detected at -120 deg C for the parent compound 5 and its 3-methyl derivative 6 whereas the twist-boat (TB) comformation becomes predominant for three derivatives, 3,3-dimethyl 7, 3-metoxy 8 and 3,3-methylmethoxy 9, as a consequence of both steric and stereoelectronic interactions.Furthermore, in the case of 8, the detailed geometry of the TB forms detected reflects on the relative importance of competing stereoelectronic (anomeric and gauche) effects.