The Use of Ureates as Activators for Samarium Diiodide.
A novel mode of SmI2 activation has been developed using ureates as reaction promoters. Several ureates formed by treatment of the corresponding ureas with n-BuLi have been shown to activate SmI2 to a substantial extent toward the reduction of 1-chlorodecane. Complexes formed from SmI2 and various ureates have been shown to be useful for the reduction of a variety of organohalides, including substrates of low reactivity such as aryl fluorides. Because of ease of synthesis and low molecular weight, the conjugate base of triethylurea (TEU(-)) was of primary focus. Visible spectroscopy and reactivity data are consistent with the hypothesis that the same complex is being formed when SmI2 is combined with either 2 or 4 equiv of TEU(-), in spite of the greater reactivity of SmI2/4 TEU(-) with some alkyl halides. We propose that the active reductant is an N,O chelate formed between SmI2 and 2 equiv of TEU(-).
Department of Chemistry, Lycoming College , 700 College Place, Williamsport, Pennsylvania 17701, United States.
Chriss E
CE
McDonald
Department of Chemistry, Lycoming College , 700 College Place, Williamsport, Pennsylvania 17701, United States.
Jeremy D
JD
Ramsey
Department of Chemistry, Lycoming College , 700 College Place, Williamsport, Pennsylvania 17701, United States.
Christopher C
CC
McAtee
Department of Chemistry, Lycoming College , 700 College Place, Williamsport, Pennsylvania 17701, United States.
Joseph R
JR
Mauck
Department of Chemistry, Lycoming College , 700 College Place, Williamsport, Pennsylvania 17701, United States.
Erin M
EM
Hale
Department of Chemistry, Lycoming College , 700 College Place, Williamsport, Pennsylvania 17701, United States.
Justin A
JA
Cumens