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Synthesis of New Water‐Soluble Atropisomeric Ligands Derived from the MeOBIPHEP Skeleton: Applications for Asymmetric CH Bond Formation and Mechanistic Studies
Author(s) -
Leseurre Lucie,
Püntener Kurt,
Genêt JeanPierre,
Scalone Michelangelo,
Michelet Véronique
Publication year - 2011
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201100535
Subject(s) - chemistry , ruthenium , ligand (biochemistry) , catalysis , asymmetric hydrogenation , solubility , solvent , carboxylate , substrate (aquarium) , transfer hydrogenation , combinatorial chemistry , base (topology) , enantioselective synthesis , organic chemistry , receptor , mathematics , geology , mathematical analysis , biochemistry , oceanography
We have extended the methodology developed for the preparation of atropisomeric chiral ligands derived from the MeOBIPHEP ligand to water‐soluble ones. The hydrophilic ligands bearing sodium carboxylate and methylammonium chloride moieties were easily synthesized under mild conditions in a short sequence and in high yields. Their solubility and acid/base properties were also determined. The ruthenium(II) catalysts contain‐ ing 4‐CO 2 Na‐ and 3,5‐(CO 2 Na) 2 ‐substituted MeOBIPHEP analogues showed excellent activities and led to the desired hydrogenated products derived from dimethyl itaconate and 2‐(4‐fluorophenyl)‐3‐methylcrotonic acid in ee s≥92%. An investigation of the asymmetric hydrogenation of the latter substrate in D 2 O as solvent afforded an insight into the mechanism.