NOBIN-based chiral phosphite-type ligands and their application in asymmetric catalysis

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

“…The quest for more stable and inexpensive ligands spurred the interest for bidentate heterodonor P,N­(sp 3 )-ligands. In most examples either amines − or amides − were used as N-donor groups and most studies focused on reactions of the benchmark linear substrate with dimethyl malonate as nucleophile (see Scheme ). The low selectivity of this class of ligand has been attributed to the low stereoselective coordination of the N-sp 3 group, which leads to the formation of diastereoisomeric mixtures of catalytic species.…”

Stereoselective Synthesis of Optically Pure 2-Amino-2′-hydroxy-1,1′-binaphthyls

“…Finally, the novel NOBIN synthesis provides a new access to a class of chiral phosphoric acids 23 with tunable nitrogen atoms near the active phosphate site, thereby offering an additional dimension of modulation. 24 Indeed, C-1 symmetric NOBINbased phosphoric acids 11a, 11b, 12, and 13 (Figure 5B) were prepared with high yields by standard methods (see the Supporting Information).…”

“…The removal of the chiral auxiliary from NOBINs 6 / 7 was successfully achieved by simple hydrogenolysis (H 2 , 10% Pd/C, ethyl acetate, rt), affording, for the first time, optically pure NOBINs 8 – 10 with different substituents on the binaphthalene backbone (Figure A). Finally, the novel NOBIN synthesis provides a new access to a class of chiral phosphoric acids with tunable nitrogen atoms near the active phosphate site, thereby offering an additional dimension of modulation . Indeed, C -1 symmetric NOBIN-based phosphoric acids 11a , 11b , 12 , and 13 (Figure B) were prepared with high yields by standard methods (see the Supporting Information).…”

First Tetradentate Diamidophosphite Based on [5,10,15,20-Tetrakis(4-hydroxyphenyl)porphyrinato]zinc: Synthesis, Spectral Features, Coordination, and Application in Asymmetric Pd-Catalyzed Reactions

“…To examine the complexing capacity of tetradiamidophosphite 2, two coordination reactions were investigated. In particular, reaction of 2 with Pd(COD)Cl 2 (our standard precursor, [39,56,57,62] COD -cycloocta-1,5-diene) proceeded in CD 2 Cl 2 and surprisingly resulted in insoluble polymeric residue. In order to shed light on the coordination properties of 2, we carried out the investigation of the ruthenium(II) complex obtained from the ligand.…”

“…[22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] We have previously reported the preparation of a series of chiral ligands -phosphorous acid derivatives, which were successfully applied in Pd-catalyzed allyl substitution reactions. [38][39][40][41][42][43] In those cases, porphyrins were used both as achiral additives [38][39][40][41] to increase enantioselectivity, and as starting substrates for phosphorylation. [42][43][44] In a preliminary communication, [44] we reported the synthesis of the first tetradentate diamidophosphite 1 (Figure 1) and its application in asymmetric Pd-catalyzed alkylation of cinnamyl acetate.…”