Mandyphos

The parent ligand 1 was first reported by Schwink and Knochel and was later described as one of a class of FERRIPHOS ligands. Later publications rebranded the following structures differing only in the nature of the phosphorus substituents as MandyPhos ligands. The following lists reactions, organised by metal (Pd, RhRu, Ir, Cu, Ni) for which the application of these ligands has resulted in >80% ee.

MandyPhos-Ligands

Palladium

Pd-Cross-coupling CEJ98-4-950

PP-MandyPhos_CEJ98-4-950

 

Rhodium

Rh-Hydrogenation TA98-10-375

PP-Mandyphos_TA99-10-375

TA04-15-2299

PP-MandyPhos_TA04-15-2299

Enamide MAC (methyl α-acetamidocinnamate) also hydrogenated (H2 – 1 bar) to give product in 99% ee with Mandyphos-1 and [Rh(NBD)2]BF4 in biphasic 1 : 1 [omin]BF4/H2O – see ASC04-346-1481.

ASC09-351-1423

PP-MandyPhos_ASC09-351-1423

Absolute configuration assigned by comparison to data in CEJ09-15-10983. Josiphos-3 has also been applied to this reaction.

CC12-48-9852

PP-MandyPhos_CC12-48-9852

 

Rh – Alkylative ring opening Angew14-53-5951

PP-MandyPhos_Angew14-53-5951

 

Ruthenium

Ru – Hydrogenation TA04-15-2299

PP-MandyPhos_Ru_TA04-15-2299

 

Iridium

Ir – Transfer hydrogenation CEJ08-14-10388

PP-MandyPhos_CEJ08-14-10388

Absolute configuration assigned by comparison to the result obtained for the reduction under the 1% Ir/ligand conditions of acetophenone [72% ee (S)].

 

Copper

Cu – Beta borylation Angew08-47-145

PP-MandyPhos_Angew08-47-145_1

Similar ee values obtained with Josiphos-1.

CEJ09-15-1939

PP-MandyPhos_CEJ09-15-1939

Josiphos-1 also applied successfully to this reaction (more examples).

Nickel

Ni – Lactam C-acylation JACS16-138-8997

PP-MandyPhos_JACS16-138-8997_1