A Novel Amphiphilic Chiral Ligand Derived from <scp>d</scp>-Glucosamine. Application to Palladium-Catalyzed Asymmetric Allylic Substitution Reaction in an Aqueous or an Organic Medium, Allowing for Catalyst Recycling

Hashizume, Tomohiro; Yonehara, Koji; Ohe, Kouichi; Uemura, Sakae

doi:10.1021/jo000305w

Cited by 76 publications

(18 citation statements)

References 50 publications

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“…22 Recovery of homogeneous catalysts has been carried out by modification of bis(oxazolines) with fluorinated ponytails 23 or by functionalization of a phosphite/oxazoline derived from D-glucosamine with amino groups, allowing extraction at different pH. 24 In both cases recycling problems were found either in activity or enantioselectivity.…”

Section: Introductionmentioning

confidence: 99%

Tridentate chiral NPN ligands based on bis(oxazolines) and their use in Pd-catalyzed enantioselective allylic substitution in molecular and ionic liquids

et al. 2011

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Section: Introductionmentioning

confidence: 99%

Tridentate chiral NPN ligands based on bis(oxazolines) and their use in Pd-catalyzed enantioselective allylic substitution in molecular and ionic liquids

et al. 2011

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“…A similar pH-controlled catalyst separation technique was used in the allylic alkylation of allyl acetates catalyzed by 17, which was derived from ligand 8 and [Pd(COD)(η 3allyl)] + BF 4 -(eq 16) [111]. The quaternary ammonium catalyst (17, R = Me) gave good yields (85%) and enantioselectivity (83% ee) for the allylic substitution of 4 and 2,4-pentanedione in 4:1 acetonitrile:water.…”

Section: Triarylphosphines With Other Ionic Modificationsmentioning

confidence: 99%

Palladium-Catalyzed Cross-Coupling in Aqueous Media: Recent Progress and Current Applications

Shaughnessy¹,

DeVasher²

2005

COC

179

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Water has attracted significant attention as an alternative solvent for homogeneous metal-catalyzed reactions because it is a non-toxic, nonflammable solvent that can allow for simplified recovery of homogeneous catalysts. The use of water as a solvent in palladium-catalyzed cross-coupling reactions is of great academic and industrial interest. Palladium-catalyzed coupling reactions are powerful methods to make carbon-carbon and carbon-heteroatom bonds under mild conditions. Separation of the catalyst from the organic product can be very difficult; however, constraining the catalyst to the aqueous-phase of an aqueous-biphasic solvent system can potentially simplify catalyst recovery. This review will focus on recent developments in the design and application of aqueous-phase, palladium-catalyzed coupling reactions over the period from 2000, through late 2004. A variety of new hydrophilic ligand architectures have been introduced recently that provide significantly more active catalysts towards industrially relevant aryl bromides and chlorides. Stille CouplingRSiX3 L n Pd(Cat) Hiyama Coupling

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“…12 This is an inter esting fact since, e.g., optically active cationic phosphinites have been successfully used in asymmetric hydrogenation and allylic substitution. 13, 14 Here we describe the synthesis of chiral P mono dentate cationic phosphite from an accessible quaternized amino alcohol and successful use of this ligand in Rh catalyzed asymmetric hydrogenation.…”

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confidence: 99%

First chiral phosphite with a quaternary ammonium fragment: Synthesis and use in Rh-catalyzed asymmetric hydrogenation

et al. 2006

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The first representative of chiral P monodentate phosphite ligands containing quaternary ammonium substituents and its rhodium complex [Rh(COD)(L) 2 ]BF 4 (COD is 1,5 cyclo octadiene) were obtained. The use of this ligand in Rh catalyzed asymmetric hydrogenation of prochiral methyl esters of unsaturated acids allowed one to achieve optical yields up to 99%.Hydrogenation of prochiral compounds catalyzed by transition metal complexes belongs to the most signifi cant asymmetric transformations because it involves in expensive molecular hydrogen and produces no side reac tions. A further development of this branch necessitates perfection of the ligand pool. First of all, this refers to phosphite type compounds, which differ from conven tional phosphines in synthetic accessibility, oxidation re sistance, and high ligating power. 1 It is also important that chiral phosphites are inexpensive. For instance, the price for phosphite derivatives of BINOL (BINOL is 2,2´ dihydroxy 1,1´ binaphthyl) was only 2% of the price of the well recognized diphosphine ligand BINAP. 2 In recent years, perfect results have been reached by using P monodentate phosphites and phosphoramidites in enantioselective Rh catalyzed hydrogenation, 1-5 Cu catalyzed conjugated addition, 6 Ir and Pd catalyzed allylation, Pd catalyzed hydrosilylation-oxidation, and Ru catalyzed hydrogenation of ketones. 7-10The synthesis and catalytic properties of achiral ionic phosphites are well studied (see Ref. 11 and references therein), while data on the use of phosphites as chiral ionic ligands are virtually lacking. The sole example we know is phosphite derivatives of (1R,2R) trans diamino cyclohexane containing carbene imidazolium fragments, which have been employed in Pd catalyzed allylic substi tution and Ir catalyzed hydrogenation. 12 This is an inter esting fact since, e.g., optically active cationic phosphinites have been successfully used in asymmetric hydrogenation and allylic substitution. 13,14Here we describe the synthesis of chiral P mono dentate cationic phosphite from an accessible quaternized amino alcohol and successful use of this ligand in Rh catalyzed asymmetric hydrogenation. Results and DiscussionThe starting synthon 1 containing an alkylammonium fragment was prepared by quaternization of 2 (dimethyl amino)ethanol with heptyl bromide followed by replace ment of the counteranion in intermediate product 2 (Scheme 1). Its direct phosphorylation in CH 2 Cl 2 gave novel cationic P monodentate chiral phosphite 3.Ligand 3 is well soluble in CH 2 Cl 2 , CHCl 3 , acetone, and acetonitrile and is fairly resistant to hydrolysis. In particular, it is acceptable to separate compound 3 from its by product triethylamine hydrochloride by extraction with water from the reaction mixture in CH 2 Cl 2 .A reaction of P monodentate phosphite 3 (2 equiv.) with [Rh(COD) 2 ]BF 4 afforded the corresponding cationic rhodium complex 4 (see Scheme 1) identified from 31 P NMR, ESI MS, and elemental analysis data (see Ex perimental).Phosphite 3 and its complex 4 were tes...

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A Novel Amphiphilic Chiral Ligand Derived from d-Glucosamine. Application to Palladium-Catalyzed Asymmetric Allylic Substitution Reaction in an Aqueous or an Organic Medium, Allowing for Catalyst Recycling

Cited by 76 publications

References 50 publications

Tridentate chiral NPN ligands based on bis(oxazolines) and their use in Pd-catalyzed enantioselective allylic substitution in molecular and ionic liquids

Tridentate chiral NPN ligands based on bis(oxazolines) and their use in Pd-catalyzed enantioselective allylic substitution in molecular and ionic liquids

Palladium-Catalyzed Cross-Coupling in Aqueous Media: Recent Progress and Current Applications

First chiral phosphite with a quaternary ammonium fragment: Synthesis and use in Rh-catalyzed asymmetric hydrogenation

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