Tris 1,1,1,3,3,3-hexafluoro-2-propyl phosphite

Purification distillation under reduced pressure in an argon flow. 

Handling, Storage, and Precaution avoid contact with skin and eyes. Avoid inhalation of vapor or mist. Normal measures for preventive fire protection. Keep container tightly closed in a dry and well-ventilated place. Containers that are opened must be carefully resealed and kept upright to prevent leakage. Store in cool place. 

C-H Arylation. Tris(l,l,l,3,3,3-hexafluoro-2-propyl)-phosphite (P[OCH(CF3)2]3) serves as a ligand in C-H activation reactions of aromatic compounds. For exartple, under the catalytic influence of RhCl(CO) P[OCH(CF3)2]3 2 and Ag2C03, the direct arylation of heteroarenes and arenes takes place with iodoarenes to afford a range of biaryls in good yields and with high selectivity. Thiophenes (eq 1), furans, pyrroles, indoles, and alkoxybenzenes are viable in this reaction. Instead of heteroarenes or arenes, allylsilanes also react with iodoarenes in the presence of RhCl(CO) P[OCH(CF3)2]3 2 catalyst to furnish the corresponding arylation product (eq 2)  

Ag2C03 in the arylation of thiophenes with iodoarenes. This is a remarkably general phenomenon, applicable to unsubstituted, monosubstituted, and disubstituted thiophene derivatives, as well as thiophene-containing fused aromatic compounds (eq 3).  

Cyclodimerization and Cycloaddition. Tris(l,l,l,3,3,3-hexafluoro-2-propyl)phosphite serves as a ligand in Ni-catalyzed cyclodimerization reactions as well as Rh- or Ni-catalyzed [4-f2] cycloaddition processes. The first example is Ni-catalyzed dimerization of isoprene with tris(l,l,l,3,3,3-hexafluoro-2-propyl) phosphite ligand. The main product is l,4-dimethyl-4-vinyl-cyclohexane (eq 4). 

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Cleavage of this group is achieved with tetramethylguanidinium syn-2-pyridinecarboxaldoxime. Tris(hexafluoro-2-propyl) phosphites are sufficiently reactive to undergo transesterification with alcohols in a stepwise fashion. ... 

Based on the precedent of Van Leeuwen and Roobeek, livinghouse and co-workers screened a variety of electron-deficient phosphine/phosphite ligands for the rhodium-catalyzed [4-1-2] reaction, which provided an alternative catalyst system for the formation of 5,6- and 6,6-ring systems [13]. The most notable of these was the tris-(hexafluoro-2-propyl) phosphite-modified rhodium complex, which was applicable to both carbon- and oxygen-tethered substrates, and also provided the first example of a facial-directed diastereoselective intramolecular rhodium-catalyzed [4-i-2] reaction (Eq. 4). 

The authors have also demonstrated that the chemoselective binding of the Rh catalyst to the allene r-system could be altered by changing the electronic property of the catalyst system. Employing tris(hexafluoro-2-propyl)phosphite as the additive, the Rh catal3rst selectively reacted with the terminal olefin of the allene 98 to furnish the 6-6-fiised ring product 99, which is analogous to the nickel-catalyzed reaction (97) (Scheme 50). 

With a common nickel(O) catalyst, prepared by the reduction of Ni(acac)2 with Et2A10Et in the presence of tris(l,1,1,3,3,3-hexafluoro-2-propyl)phosphite, the dienyne undergoes stereo-controlled cycloaddition (eq 10). Nickel(O) also catalyzes intramolecular [4+2] cycloadditions of nitrogen-containing dienynes, providing a novel method for the synthesis of hydroisoquinolines (eq 11). A typical Ni(0) catalyst derived from Ni(cod>2 and tris(l,l,l,3,3,3-hexafluoro-2-propyl)phosphite at room temperature. 

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