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                            PhosphonicS Oxidation Catalysts

                            Allylic and benzylic oxidations, alcohol oxidations, sulfoxidations and epoxidations are key chemical transformations. However these reactions, generally conducted by the use of stoichiometric concentrations of inorganic oxidants, suffer from significant environmental and safety drawbacks which have restricted their use on process and manufacturing scale.  Widely-used oxidising reagents include potassium permanganate, manganese dioxide, chromium trioxide, potassium chromate, potassium dichromate and peracids. These hazardous reagents present handling challenges as well as producing large volumes of toxic waste that is becoming increasingly costly to treat and dispose of in an  environmentally-friendly manner.

                            Purification Simplified

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                            Difficulties in the work-up of these oxidation reactions as well as in the purification of the products, particularly from metal residues, are also often encountered.  Whilst highly efficient metal scavenging technologies are available, a more efficient approach is to employ heterogeneous catalysts which do not contaminate the product and which do not generate hazardous waste.

                            PhosphonicS™ heterogeneous oxidation catalysts cleanly, efficiently and selectively perform key oxidative transformations (right), using cheap, environmentally benign oxidants such as hydrogen peroxide.  Reaction products are afforded without metal contamination and the catalyst can be recovered by filtration for re-use.

                            PhosphonicS heterogeneous oxidation catalysts are available separately or in kit form for initial screening (kit contains Co, Cr, VO, Ce and Mn catalysts, in either 10 g or 25 g format.  Most metals in common oxidation states can be provided as immobilised catalysts on request.
                            Catalytic metal Product code Substrate(s) Product(s) Suitable oxidants Leading references
                            Cobalt (II) POCo Allylic CH2
                            Benzylic CH2
                            Enones
                            Aromatic ketones
                            tBuOOH Tet. Lett., 2003, 44, 22, 4283
                            Tet. Lett., 2004, 45, 23, 4465
                            Chromium (III) POCr Allylic CH2
                            Benzylic CH2
                            Sulfides
                            Enones
                            Aromatic ketones
                            Sulfoxides
                            tBuOOH
                            NaBrO3
                            Manganese (II) POMn Allylic CH2
                            Benzylic CH2
                            Enones
                            Aromatic ketones
                            tBuOOH
                            Vanadyl (IV) POVO Allylic alcohols
                            α-hydroxyacids
                            Sulfides
                            Enones
                            α-ketoacids
                            Sulfoxides
                            tBuOOH, NaBrO3 or H2O2 Tet. Lett., 2004, 45, 23, 4465
                            Tet. Lett., 2006, 47, 46, 8017
                            Cerium (IV) POCe Alcohols
                            Sulfides
                            Ketones; carboxylic acids
                            Sulfoxides
                            tBuOOH or NaBrO3 Tet. Lett., 2003, 44, 4, 769
                            Tet. Lett., 2005, 46, 25 4365

                            Example Procedures

                            Typical procedures for laboratory screening reactions can be provided; please email for details.