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[NiCl 2 (dppp)]‐Catalyzed Cross‐Coupling of Aryl Halides with Dialkyl Phosphite, Diphenylphosphine Oxide, and Diphenylphosphine
Author(s) -
Zhao YuLong,
Wu GuoJie,
Li You,
Gao LianXun,
Han FuShe
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201103723
Subject(s) - diphenylphosphine , diphenylphosphine oxide , aryl , catalysis , chemistry , phosphine , medicinal chemistry , phosphine oxide , halide , catalytic cycle , coupling reaction , oxidative addition , organic chemistry , photochemistry , alkyl
We present a general approach to CP bond formation through the cross‐coupling of aryl halides with a dialkyl phosphite, diphenylphosphine oxide, and diphenylphosphane by using [NiCl 2 (dppp)] as catalyst (dppp=1,3‐bis(diphenylphosphino)propane). This catalyst system displays a broad applicability that is capable of catalyzing the cross‐coupling of aryl bromides, particularly a range of unreactive aryl chlorides, with various types of phosphorus substrates, such as a dialkyl phosphite, diphenylphosphine oxide, and diphenylphosphane. Consequently, the synthesis of valuable phosphonates, phosphine oxides, and phosphanes can be achieved with one catalyst system. Moreover, the reaction proceeds not only at a much lower temperature (100–120 °C) relative to the classic Arbuzov reaction (ca. 160–220 °C), but also without the need of external reductants and supporting ligands. In addition, owing to the relatively mild reaction conditions, a range of labile groups, such as ether, ester, ketone, and cyano groups, are tolerated. Finally, a brief mechanistic study revealed that by using [NiCl 2 (dppp)] as a catalyst, the Ni II center could be readily reduced in situ to Ni 0 by the phosphorus substrates due to the influence of the dppp ligand, thereby facilitating the oxidative addition of aryl halides to a Ni 0 center. This step is the key to bringing the reaction into the catalytic cycle.