Triphenylarsine, reaction+carbonyls

The addition of LiCl and Cul, and triphenylarsine as ligand are required to suppress side-reactions in the carbonylative cross-coupling of geminally substituted alkenyl triflate in the synthesis of sarcodictyin. Stereochemical configuration of the double bond of organotin compound was completely lost in this reaction (Equation (5)). " ... 

Semistabilized ylides such as benzylidene- (55) or methylene- (59) triphenylarsorane reacted with carbonyl compounds in ether to give olefins as well as oxiranes. For example, reaction of methylene triphenylarsorane with benzophenone gave, besides triphenylarsine oxide... 

The first stable cobalt carbonyl cation to be prepared was traw-bis(tri-phenylphosphine)cobalt tricarbonyl cation (219), obtained by disproportionation of cobalt carbonyl and carbonylation of Co(PPh3)2I2. Hieber and Freyer examined the reaction of triphenylphosphine with cobalt carbonyl (129, 130). The product from the reaction with triphenylarsine and triphenylstibine is a salt at low temperatures, but, on warming, a redox reaction occurs, producing a substituted cobalt carbonyl (129). Thus the reaction scheme is... 

In the benzenoid 5-position in pyrimidines, ketones have also been prepared from carbonyl chlorides using the Sn-Pd methodology (Scheme 29). 5-(2-Pyrrolylcarbonyl)pyrimidine (138) is available from pyrimidine-5-carbonyl chloride in a Pd-catalyzed reaction with the corresponding 2-pyrrolylstannane. The catalyst was ligated to triphenylarsine, since the complex with triphenylphosphine was not active enough for a satisfactory conversion in this reaction. When the polarization of the reactants is reversed, however, triphenylphosphine is a good ligand for the Pd-catalyst (see below). 

Some acrylylcobalt carbonyl derivatives have been investigated. Treatment of Na[Co(CO)4] with acrylyl chloride appears to give an unstable acrylylcobalt tricarbonyl derivative which could not be isolated in the pure state but which was identified from its infrared spectrum 239). If this acrylylcobalt carbonyl complex is treated in situ with triphenylphosphine, evolution of one mole of carbon monoxide occurs and the complex CH2= CHCOCo(CO)2P(C6Hs)3 is obtained as a moderately stable yellow solid 242). Similar complexes were observed in the reactions of the crude acrylyl-cobaltcarbonyl complex with triphenylarsine, tri-/>-anisylphosphine, tri-butylphosphine, and trimethyl phosphite, but these were not isolated in the pure state (239). Treatment of Na[Co(CO)4] with acrylyl chloride under much more vigorous conditions gives a low yield of a purple compound CH2=CHCCo3(CO)9 117) related to compounds discussed below. 

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