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Synthesis of Aryl and Arylmethyl Phosphonates by Cross‐Coupling of Aryl or Arylmethyl Halides (X = I, Br and Cl) with Diisopropyl H‐Phosphonate
Author(s) -
Xu Kai,
Hu Hao,
Yang Fan,
Wu Yangjie
Publication year - 2013
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201201230
Subject(s) - chemistry , aryl , phosphonate , catalysis , palladium , medicinal chemistry , halide , base (topology) , substrate (aquarium) , combinatorial chemistry , organic chemistry , alkyl , mathematical analysis , oceanography , mathematics , geology
An efficient and generally applicable protocol for the palladacycle‐catalysed arylation or K 2 CO 3 ‐promoted arylmethylation of diisopropyl H‐phosphonate has been developed. The remarkable features of the palladacycle‐catalysed arylation reaction include wide substrate scope (aryl iodides, bromides and chlorides), significant shortening of the reaction time (2 or 3 h) and a low catalyst loading of 1 mol‐%. Note that with the base K 2 CO 3 as promoter, arylmethylation could be achieved without any palladium catalyst. Moreover, the first example of a palladium‐catalysed phosphonation of inactive electron‐rich aryl chlorides with t BuOK as the base has been realized. This result could be considered an important improvement and complement to earlier work of Montchamp and Han, whose catalytic systems are typically compatible with electron‐deficient and electron‐neutral aryl chlorides.