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- W1964777713 abstract "A mechanistic study on the conjugate addition of diethylzinc to cyclohexenone catalyzed by various chiral PIII ligands, provides new insights into its mechanism. Complete in situ conversion of the catalytic amount of Cu(OTf)2 into CuI species by excess ZnEt2 is demonstrated by EPR spectroscopy. Experimental evidence is presented in favor of a critical ternary 1:1:1 complex between enone, Et2Zn and catalyst, supporting a rate-limiting reductive elimination or carbocupration from a preformed mixed Cu/Zn cluster carrying one- or two-ligand molecules. A crystal structure has been obtained for a CuIL2 complex, which shows catalytic turnover on addition of reagent and substrate. NMR spectroscopic analyses and VT experiments reveal that steric hindrance may prevent complexation of a second ligand molecule on the CuI cation, leading to extremely fast precatalysts based on CuX.L species." @default.
- W1964777713 created "2016-06-24" @default.
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- W1964777713 date "2004-11-18" @default.
- W1964777713 modified "2023-10-17" @default.
- W1964777713 title "On the Role of PIII Ligands in the Conjugate Addition of Diorganozinc Derivatives to Enones" @default.
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- W1964777713 doi "https://doi.org/10.1002/chem.200400316" @default.
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