442905-37-5Relevant academic research and scientific papers
Electronic properties of furyl substituents at phosphorus and their influence on 31P NMR chemical shifts
Ackermann, Marco,Pascariu, Aurelia,Hoecher, Thomas,Siehl, Hans-Ullrich,Berger, Stefan
, p. 8434 - 8440 (2007/10/03)
The electronic properties of 2-furyl and 3-furyl substituents attached to phosphanes and phosphonium salts were studied by means of IR spectroscopy and experimental and computational 31P NMR spectroscopy. The heteroaromatic systems proved to be electron withdrawing with respect to phenyl substituents. However, phosphorus atoms with attached furyl substituents are strongly shielded in NMR. The reason for this phenomenon was studied by solid state 31P MAS NMR experiments. The chemical shift tensor was extracted, and the orientation within the molecules was determined. The tensor component σ33, which is effected the most by furyl systems, is oriented perpendicular to the P-C bonds of the substituents. P-furyl bonds are shorter than P-phenyl bonds. We assume therefore a lower ground-state energy of the molecules, because of the electron withdrawing properties of the 2-furyl systems. The σpara component of the 31P NMR magnetic shielding is therefore smaller, which results in an overall increase of the magnetic shielding.
A Wittig reaction with 2-furyl substituents at the phosphorus atom: Improved (Z) selectivity and isolation of a stable oxaphosphetane intermediate
Appel, Marco,Blaurock, Steffen,Berger, Stefan
, p. 1143 - 1148 (2007/10/03)
Wittig reactions with ylides bearing one, two or three 2-furyl groups directly bound to the phosphorus atom have been studied. Greatly improved (Z)-alkene selectivities of up to 98:2 could be observed if 2-furyl groups were present. Monitoring of the reactions by NMR spectroscopy revealed only oxaphosphetane intermediates, which became more stable with increasing number of 2-furyl substituents bound to the phosphorus atom. Oxaphosphetane 10d, with three furyl groups, was successfully isolated, and the results of a crystal structure analysis are presented. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
