Phosphinooxazolines

Phosphinooxazolines (often abbreviated PHOX) are a class of chiral ligands used in asymmetric catalysis. Their complexes are particularly effective at generating single enatiomers in reactions involving highly symmetric transition states, such as allylic substitutions, which are typically difficult to perform stereoselectively. The ligands are bidentate and have been shown to be hemilabile with the softer P‑donor being more firmly bound than the harder N‑donor.

The synthesis of phosphinooxazolines is modular and it is not normally necessary to introduce the phosphine and oxazoline moieties in any particular order. However while examples exist of the phosphine being introduced first, it is more common to see the synthesis of a phenyloxazoline which is subsequently combined with a source of diphenylphosphine. Methods for doing this depend on the nature of the subsituent in the X position:

Of these methods the copper iodide catalysed reaction method is by far the simplest to carry out, as it does not require the synthesis of discrete anionic or organometallic species and is able to couple a wide range of materials in good to excellent yields.

Phosphinooxazolines are able to influence both the enantioselectivity and regioselectivity of a range of metal catalysed reactions. In reactions involving symmetric transition states these properties work in concert to induce asymmetry and thus promote the formation of a single product. Enantioselectivity is controlled by the chirality of the ligand which is normally located on the oxazoline ring, however the P-centre may also be stereogenic. Regioselectivity is controlled by variety of steric and electronic factors the most important of which being a form of trans effect, in which atoms complexed trans to the P‑atom become more electrophilic than ones located trans to the N‑atom. This is caused by the P‑atom engaging in back bonding, as it is a π‑electron acceptor.

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