1354629-29-0Relevant articles and documents
PRODUCTION METHOD FOR BI(HETERO)ARYL(THIO)ETHER COMPOUND
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Paragraph 0111-0115; 0117, (2017/10/31)
PROBLEM TO BE SOLVED: To provide a method for synthesizing a bi(hetero)aryl(thio)ether compound at low cost without discharging halogen-derived waste. SOLUTION: The production method includes, for example as shown in the following formula, reacting a (thio)ester compound represented by formula (1) in the presence of a nickel catalyst (or a palladium catalyst) as well as a ligand compound to produce bi(hetero)aryl(thio)ether compound represented by formula (2). [Ar and Ar' are each independently a substituted/unsubstituted aryl group or heteroaryl group; Y is O or S.]. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
Etherification of functionalized phenols with chloroheteroarenes at low palladium loading: Theoretical assessment of the role of triphosphane ligands in C-O reductive elimination
Platon, Melanie,Cui, Luchao,Mom, Sophal,Richard, Philippe,Saeys, Mark,Hierso, Jean-Cyrille
supporting information; experimental part, p. 3403 - 3414 (2012/02/02)
The present study highlights the potential of robust tridentate ferrocenylphosphanes with controlled conformation as catalytic auxiliaries in C-O bond formation reactions. Air-stable palladium triphosphane systems are efficient for selective heteroaryl ether synthesis by using as little as 0.2 mol% of catalyst. These findings represent an economically attractive and clean etherification of functionalized phenols, electron-rich, electron-poor and para-, meta- or ortho-substituted substrates, with heteroaryl chlorides, including pyridines, hydroxylated pyridine, pyrimidines and thiazole. The etherification tolerates very important functions in various positions, such as cyano, methoxy, amino, and fluoro groups, which is useful to synthesize bioactive molecules. DFT studies furthermore demonstrate that triphosphane ligands open up various new pathways for the C-O reductive elimination involving the third phosphane group. In particular, the rate for one of these new pathways is calculated to be about 1000 times faster than for reductive elimination from a complex with a similar ferrocenyl ligand, but without a phosphane group on the bottom Cp-ring. Coordination of the third phosphane group to the palladium(II) center is calculated to stabilize the transition state in this new pathway, thereby enhancing the reductive elimination rate. Copyright
