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Hatakeyama T.,International Research Center for Elements Science | Yoshimoto Y.,International Research Center for Elements Science | Ghorai S.K.,International Research Center for Elements Science | Nakamura M.,International Research Center for Elements Science
Organic Letters | Year: 2010

In the presence of N,N,N′,N′-tetramethylethylenediamine (TMEDA) as an additive, easily prepared and handled N-chloroamines react with aryl Grignard reagents to give a variety of arylamines in good to excellent yields. Functional groups such as ester and nitrile are compatible under the reaction conditions (Figure Presented). © 2010 American Chemical Society.


Ozawa F.,International Research Center for Elements Science | Nakajima Y.,Japan National Institute of Advanced Industrial Science and Technology
Chemical Record | Year: 2016

This account summarizes our recent studies on PNP-pincer-type phosphaalkene complexes. Phosphaalkenes with a P=C bond possess an extremely low-lying π* orbital and have a marked tendency to engage in strong π back-bonding with transition metals. This particular ligand property provides PNP-pincer complexes with unique structures and reactivities. 2,6-Bis(phosphaethenyl)pyridine leads to the isolation of coordinatively unsaturated complexes of Fe(I) and Cu(I); the former adopts a trigonal monopyramidal configuration, whereas the latter has a strong affinity for PF6- and SbF6- as non-coordinating anions. Unsymmetrical PNP-pincer-type phosphaalkene complexes of Ir(I) bearing a dearomatized pyridine unit instantly cleave the N-H bond of NH3 and the C-H bond of MeCN at room temperature. The dearomatized iridium complexes catalyze the dehydrative coupling of amines with alcohols to afford N-alkylated amines and imines in high yields. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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