404344-80-5Relevant academic research and scientific papers
Reactivity of sterically unencumbered transient nitrilium phosphanylide complexes towards 1-piperidinocarbonitrile: A case study
Streubel, Rainer,Schiemann, Udo,Huy, Ngoc Hoa Tran,Mathey, Francois
, p. 3175 - 3179 (2007/10/03)
The thermal decomposition of the 7-phosphanorbornadiene complexes 6a,b in xylene at 120 °C in the presence of two equivalents of 1-piperidinocarbonitrile yielded the 2H-1,3,2-azaphosphole complexes 11a,b and the 2H-1,4,2-azaphosphole complexes 12a-c in ratios of 7:4 (11a:12a) and 1:5 (11b:12b). Remarkably, the two atropisomers 12b and 12c were obtained (ratio: 5:1) in the case of the P-phenyl-substituted 2H-1,4,2-azaphosphole complex. Interestingly, the product ratios of both reactions were approximately the same if neat 1-piperidinocarbonitrile was used as the solvent. The reaction of complexes 6a,b with CuIC1 and 1-piperidinocarbonitrile, with exclusion of light, also furnished the 2H-1,3,2-azaphosphole complexes 11a,b as the main products. In the case of complex 6a, a by-product was detected by 31P NMR spectroscopy but could not be isolated. Complexes 11a,b, 12a and 13 were purified by column chromatography at low temperature and characterized by NMR and MS spectroscopic means and elemental analysis, whereas only a 1:1 mixture of 12b and 12c could be characterized.
