A New Ligand for SmI2

This paper reports the synthesis of a 3-hydroxypropyl analog of HMPA. This ligand will be coordinated to SmI2, and kinetic studies are performed. This is worthy of study because the protonation step of the reduction mechanism, which typically occurs intermolecularly in SmI2-mediated reductions of carbonyls, will occur intramolecularly; thus, the potential exists for rate enhancement. The complex between SmI2 and the synthesized ligand, N, N, N’, N’, N’’-pentamethylphosphorotriamidic-N’’-propan-1-ol, was able to successfully reduce 1-bromodecane and 3-octanone. However, kinetic studies performed on 3-octanone revealed a rate constant that was smaller than the rate observed for the corresponding HMPA complex.