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Synthesis of Bulky Arylphosphanes by Rhodium‐Catalyzed Formal [2+2+2] Cycloaddition Reaction and Their Use as Ligands
Author(s) -
Kobatake Takayuki,
Kondoh Azusa,
Yoshida Suguru,
Yorimitsu Hideki,
Oshima Koichiro
Publication year - 2008
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200800102
Subject(s) - cycloaddition , rhodium , catalysis , chemistry , steric effects , amination , cationic polymerization , ligand (biochemistry) , combinatorial chemistry , coupling reaction , palladium , medicinal chemistry , organic chemistry , biochemistry , receptor
Treatment of 1‐alkynylphosphane sulfides with 1,6‐ or 1,7‐diynes in the presence of a cationic rhodium catalyst results in a formal [2+2+2] cycloaddition reaction to afford the corresponding aromatic phosphane sulfides. The aromatic rings formed in the cycloaddition naturally bear one or two substituents at the ortho positions to the phosphorus atom, which creates a sterically hindered environment around the phosphorus atom. The following desulfidation of the products is facile under radical conditions or with the aid of tris(dimethylamino)phosphane, providing the corresponding bulky phosphanes. Dicyclohexyl(2,6‐diphenylaryl)phosphane, which is available through this sequence, proves to serve as an efficient ligand in palladium‐catalyzed cross‐coupling amination reactions.