A phosphorus-containing chiral amidine ligand for asymmetric reactions: enantioselective Pd-catalyzed allylic alkylation

Ferrocenylphosphine–imine ligands for Pd-catalyzed asymmetric allylic alkylation

“…1 Among various chiral ligands developed for this reaction, P,N ligands have been used for a long time 2 and great progress has been made in the past decade in achieving high enantioselectivities. These P,N ligands include amino-phosphines, 3 oxazolino-phosphines, 4 pyridino-phosphines, 5 hydrazono-phosphines, 6 amidino-phosphines, 7 oxazolizino-phosphines, 8 oxazinano-phosphines, 9 and so on.…”

The First Asymmetric Halogen/Metal‐Exchange Reaction: Desymmetrization of Alcohols with Enantiotopic Bromoarene Substituents

“…Alcohols 11 and 12 as well as aminoalcohol 14 and (S)-2,2'-dihydroxy-1,1'-binaphthalene [(S)-BINOL (17 a)] were purchased. Aminoalcohols 13 a, [17] 13 b, [18] 13 c, [19] 13 d, [20] 15 a, [21] 15 b, [22] 16 a, [23] and 16 b [24] were prepared according to literature procedures, and (S)-BINOL-monoethers 17 b [25,26] and 17 c, d as well. [26] NHC precursor 21 is an elaborated 2-amino-2'-hydroxy-1,1'-binaphthalene (NOBIN) and was obtained by our recently developed synthesis [27] in 55 % overall yield, avoiding the lengthier previous synthesis.…”

The Development of Bidentate P,N Ligands for Asymmetric Catalysis

“…Variation of the phenyl substituent allowed for the evaluation of electronic effects upon the reaction, Table 14, and the use of ketene silyl acetals as harder nucleophiles was also investigated. [61,62] Subsequent testing of VALAP (192) in the conjugate addition of diethylzinc to 2-cyclohexenone gave no enantiodiscrimination. However, the preparation of derivatives with a pyridyl side-arm which allowed the ligand to act in a tridentate fashion enabled enantioselectivities of up to 91% to be obtained.…”