Di(hydroperoxy)alkane Adducts of Phosphine Oxides: Safe, Solid, Stoichiometric, and Soluble Oxidizing Agents
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The di(hydroperoxy)alkane adducts of phosphine oxides 1-9, Ph3 PO⋅(HOO)2 CMe2 , Cy3 PO⋅(HOO)2 CMe2 , Ph3 PO⋅ (HOO)2 CMeEt, Cy3 PO⋅(HOO)2 CMeEt, Cy3 PO⋅(HOO)2 CEt2 , Cy3 PO⋅ (HOO)2 C(CH2 )5 , Cy3 PO⋅(HOO)2 CMePh, (Ph2 P(O)CH2 CH2 P(O)Ph2 )⋅ ((HOO)2 CEt2 )2 , and Ph2 P(O)CH2 P(O)Ph2 ⋅(HOO)2 CMe2 , respectively, are synthesized and fully characterized by 1 H, 13 C, and 31 P NMR, and IR spectroscopies. Single crystal X-ray structures are reported for 3-9. Different one-pot synthetic pathways, starting from R3 P, R3 PO, R3 PO⋅H2 O, and R3 PO⋅H2 O2 are explored and discussed and a mechanism for the formation of the di(hydroperoxy)alkane adducts of phosphine oxides is suggested. The longevity of the adducts is tested by monitoring the oxidation of Ph3 P with quantitative NMR. The solubilities of the adducts in organic solvents are presented, and their applicability as stoichiometric oxidizing agents for the selective oxidation of sulfides to sulfoxides is reported.
author list (cited authors)
Ahn, S. H., Bhuvanesh, N., & Blümel, J.