The reaction of ketenylidenetriphenylphosphorane (Ph 3PCCO) with acidic HE (EO, N) Bonds

Article abstract of DOI:10.1080/10426507.2012.710674

The reactivity of ketenylidenetriphenylphosphorane (1) with the protic reagents 2,4,6-trimethylphenol (7), 2,6-di-tert-butyl-4-methylphenol (8), and diphenylamine (9) has been explored. Three novel carbonyl-stabilized ylides have been synthesized and characterized. Crystal structures were obtained for Ph3PCHC(O)O(C6H2Me3) (11), Ph3PCHC(O)O(C6H2t-Bu2Me) (12), and Ph3PCHC(O)NPh2 (13), respectively. These products were then methylated in an attempt to develop a new route to low-valent carbon compounds. Crystals of [Ph3PCH(CH3)C(O) O(C6H2Me3)]I (14) were isolated and characterized but this route did not prove to be synthetically useful, at least toward the goal of preparing low-valent carbon-centered materials. Finally, 1 was also reacted with the bulky tin reagent, bis[bis(trimethylsilyl)amido]tin(II), in the presence of 2,4,6-trimethylphenol. A complex mixture of products was obtained, from which crystals of an unusual chelated tin compound (15) were isolated and characterized using X-ray crystallography.