Pseudohalides reaction with

Quite a contrasting effect was found for the solvolysis of sterically hindered palla-dium(II) complexes of the ligand Et2NCH2CH2NHCH2CH2NEt2 (= Et4dien).16 The reactions, with X = halide or pseudohalide, are... 

Treichel, Knebel, and Hess provided further data on these systems by studying reactions of [Pt(PRj)2(CNCH3)2] with various halide ions and with pseudohalides. A series of five-coordinate complexes were obtained from reactions with iodide ion (PRj = PPhj, PPh2Me, PPhMe2, PEtj), and a study was carried out to measure the stability of these complexes with respect to ligand loss 155). Stability constants for several of these complexes were obtained from spectroscopic data. Other reactants (Cl, Br, CN, SCN) generally yielded the appropriate [Pt(PRj)2(CNCH3)X] species, as expected. 

The Heck reaction, a palladium-catalyzed vinylic substitution, is conducted with olefins and organohalides or pseudohalides are frequently used as reactants [15, 16], One of the strengths of the method is that it enables the direct monofunctionalization of a vinylic carbon, which is difficult to achieve by other means. Numerous elegant transformations based on Heck chemistry have been developed in natural and non-natural product synthesis. Intermolecular reactions with cyclic and acyclic al-kenes, and intramolecular cyclization procedures, have led to the assembly of a variety of complex and sterically congested molecules. 

TV-phenylbenzohydroxamic acid, 506, phthalocyanines, 865 polypyrazolylborates, 248 porphyrins, 823 pseudohalides, 228 Titanium(III) complexes octaethylporphyrin reaction with dioxygen, 325 Titanium(IV) complexes 1,3-diketones, 376 triazines... 

Diorganotetrapseudohalotellurates(IV) were obtained from tetrachlorotellurates(TV) or tetraiodotellurates(IV) via exchange reactions1 2. Silver cyanide was used to exchange chloride for cyanide1. Chloride and iodide were replaced by pseudohalides in reactions with potassium cyanate, potassium thiocyanate, or potassium azide. 

Halide ion Y" in the form of soluble tetraalkylammonium salts can in some cases displace halide ion X forming a mixed-halogen adduct. However, the method has met with variable success. It is successful with tetrahaloborate ions (80) and with Me3N BI3 (9). A similar reaction with insoluble silver halides or pseudohalides has also given mixed adducts (43). 

Similarly, reactions of C B(OMe)2 4 with Hg(OAc)2 afforded C(FIgOAc)4 125 a series of tetra-mercuro-methanes, C(HgX)4 (X = C1, Br, I, CN, SCN) has been obtained from reactions of C Hg(OAc) 4 with halides or pseudohalides.126 In turn, the acetoxy compounds derived from Hofmann s base , previously thought to contain a C2 unit, are now believed to be a polymeric oxonium ion formed by condensation of C Hg(OH) 4. Treatment of this compound with acetic or trifluoroacetic acids afforded C Hg(02R) 4 (R = Me, CF3). Extensive spectroscopic studies of these derivatives have been carried out. Further reactions with... 

For the ketone synthesis via the present protocol, acid chlorides are useful precursors, in deed. Nevertheless, carbonylative cross coupling with organic halides is strategically the most simple and direct way to this purpose. The palladium-catalyzed carbonylative cross-coupling reaction with various organic halides has been extensively investigated, because of its merits from synthetic as well as phenomenal point of view. Acid chlorides are not always readily available, and their preparation is not always compatible with many sensitive functionalities. Therefore the development of this type of reaction widens the scope of the ketone synthesis in the present protocol because of the ready availability and storability of organic halides and pseudohalides. 

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