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, Rh, Ru, Ir, Cu, Ni) for which the application of these ligands has resulted in >80% ee. ACE = Asymmetric Catalytic Efficiency. Literature covered until end 2017 (16 entries).
Pd – Conjugative cross-coupling Science16-351-70
The presence of lithium halide salts (even at 1-2 mol%) markedly erodes conjugative coupling efficiency. Later found that this inhibition may be overcome by the addition of NaOTf or KOTf such that vinyllithium may be generated from the addition of t-BuLi (2 eq.) to vinyl bromide and conjugative cross-coupling carried out with 2.2 eq. of KOTf. See JACS17-39-3153.
Allyl boron reagents containing 1- or 2-(Z)-substituents resulted in ee values <80%. Halide free vinyllithium employed generated from tetravinylstannane by Li-Sn exchange. Vinyl magnesium chloride and vinyllithium generated from vinyl bromide (+ 2 eq. t-BuLi) also used successfully provided 2 eq. of NaOTf or KOTf added, respectively (and at 2 mol% catalyst loading).
Absolute configuration assigned by comparison to data in CEJ09-15-10983. Josiphos-3 has also been applied to this reaction.
Rh – Asymmetric ring opening JACS06-128-6837
The ligand used is described as Ferriphos and is closely related to Mandyphos-1. It is reasonable to suggest that the latter woud give similar results (e.g. – see next entry). Ferriphos not commercially avaialble. For synthesis see TA99-10-375 and earlier work by Hayashi in CC89-495.
Ru – Hydrogenation TA04-15-2299
Diastereoselective hydrogenation in a biphasic system with the product isolated after separation of the aqueous phase from ionic liquid [EMIN][NTf2] followed by addition of HCl(aq). Catalyst phase reused for an additional 6 cycles with little loss of selectivity and conversion (so ACE = approximately 700).
Ir – Transfer hydrogenation 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)].
Cu – Beta borylation Angew08-47-145
Similar ee values obtained with Josiphos-1.
Josiphos-1 also applied successfully to this reaction (more examples).
Ni – Lactam C-acylation JACS16-138-8997