Chiral phosphinoazomethinylate salts as new ‘one-step available’ ligands for copper-catalyzed asymmetric conjugate addition

Enantioselective 1,6‐Conjugate Addition of Dialkylzinc Reagents to Acyclic Dienones Catalyzed by Cu‐DiPPAM Complex—Extension to Asymmetric Sequential 1,6/1,4‐Conjugate Addition

“…In our quest for the design of readily available and efficient chiral ligands for asymmetric organometallic catalysis, we have recently developed “one‐step and quantitatively available” ligands—the diphenylphosphinoazomethinylate salts (DiPPAM) 11. The DiPPAM L2 (Figure 1), which is structurally related to “small peptide ligands”,12 has already proved its efficiency for copper‐catalyzed 1,6‐ACA of di alkylzinc reagents to cyclic dienones 5c.…”

“…In our quest for the design of readily available and efficient chiral ligands for asymmetric organometallic catalysis, we have recently developed "one-step and quantitatively available" ligands-the diphenylphosphinoazomethinylate salts (DiPPAM). [11] The DiPPAM L2 (Figure 1), which is structurally related to "small peptide ligands", [12] has already proved its efficiency for copper-catalyzed 1,6-ACA of di alkylzinc reagents to cyclic dienones. [5c, e] These results encouraged us to investigate the more challenging Cu-catalyzed 1,6-ACA of dialkylzinc reagents to linear dienones, using some chiral ligands including our DiPPAM ligand.…”

Isolation and Characterization of a Chiral η1-Allyl Palladium DIPPAM Complex: Application to the Enantioselective Pd-Catalyzed Allylic Alkylation

“…In the quest for new readily available and costless ligands that would be applicable to environmentally and economically valuable processes, we have recently synthesized a new family of ligands, the diphenylphosphinoazomethinylate salts (DIPPAM, Figure ) …”

Phosphines and related C–P bonded compounds

“…158 Both imine-formation from 2-diphenylphosphinobenzaldehyde and amide-formation from 2-diphenylphosphinobenzoic acid have found further use. New phosphines prepared from the phosphinoaldehyde include a phosphinoaryliminothiosemicarbazone, 159 1-4 nitrogen donor sites, some with additional aminophosphine functionality, 160 phosphino-imine and phosphino-amine ligands derived from D-glucosamine, 161 a series of phosphinoimines derived from chiral aminoalcohols, 162 the chiral phosphinoazomethinylate salts (114) obtained from imine formation with commercially available enantiopure a-aminoacids, 163 and the multifunctionalised ligand (115). 164 New chiral phosphinoarylamides have been prepared from 2-diphenylphosphinobenzoic acid and (S)-phenylglycinol and (S)-phenylalanine.…”