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
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 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.
| 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.