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An enantioselective synthesis of chiral alkylphosphonates bearing a β-stereogenic center, based on the Rh-catalyzed asymmetric hydrogenation of corresponding β-substituted β,γ-unsaturated phosphonates with a ferrocenebased monophosphoramidite ligand under the mild hydrogenation conditions, was developed, in which an ee value of up to 98% was obtained. [ABSTRACT FROM AUTHOR]

A new class of chiral ferrocenyl diphosphine ligands with an imidazole ring, (Rc,SFc)-ImiFerroPhos, has been prepared from acylferrocenes through a five-step transformation and successfully applied in the Rh-catalyzed asymmetric hydrogenation of various 3-aryl-substituted 2-phosphonomethylpropenoates, in which a series of chiral 3-phosphono-2-arylmethylpropanoic acid derivatives were achieved in ee values of up to 98%. [ABSTRACT FROM AUTHOR]

A new family of unsymmetrical ferrocenylethylamine-derived monophosphoramidites were synthesized and successfully applied in the Rh-catalyzed enantioselective hydrogenation of a range of enamides and α-dehydroamino acid esters, and ee values of up to 99.5% were obtained for both types of substrate. These results suggest that unsymmetrical amine-derived monophosphoramidites can also exhibit excellent enantioselectivity for a broad range of substrates, comparable to or higher than those of the most efficient symmetrical amine-derived monophosphoramidites reported thus far. [ABSTRACT FROM AUTHOR]

A series of chiral 3-aryl-4-phosphonobutyric acid esters were synthesized in high enantioselectivities (93-98% ee) via the Rh-catalyzed asymmetric hydrogenation of the corresponding 3-aryl-4-phosphonobutenoates using a P-stereogenic BoPhoz-type phosphine-aminophosphine ligand. The methodology has been successfully applied to the asymmetric synthesis of a potential GABAB antagonist, (R)-phaclofen, in high enantioselectivity. [ABSTRACT FROM AUTHOR]

An enantioselective synthesis of optically active 1-aryl or 1-alkyl substituted ethyiphosphonates, based on the first Rh- catalyzed asymmetric hydrogenation of corresponding α,β-unsaturated precursors with a P-stereogenic BoPhoz-type ligand under the mild condition, was developed, in which a wide range of 1-aryl or 1-alkyl substituted ethyiphosphonates were achieved in up to 98% ee. [ABSTRACT FROM AUTHOR]

A series of chiral β-aryl-substituted γ-amino butyric acid derivatives were synthesized in good enantioselectivities via the Cu-catalyzed asymmetric conjugate reduction of γ-phthalimido-α,β-unsaturated carboxylic acid esters using Cu(OAc)2·H2O as a catalyst precursor, (S)-BINAP as a ligand, PMHS as a hydride source, and t-BuOH as an additive. The methodology has been applied successfully to the enantioselective synthesis of a chiral pharmaceutical, (R)-baclofen. [ABSTRACT FROM AUTHOR]

A series of BoPhoz-type ligands were successfully applied in the rhodium-catalyzed asymmetric hydrogenation of a number of β-substituted or unsubstituted α-(phthalimidomethyl)acrylates, affording good to excellent enantioselectivities. The results suggested that the presence of an N-H proton in the BoPhoz backbone could significantly improve the enantioselectivity, and ligand (Sc,Rp)-1d, bearing two CF3-groups in the 3,5-position of the phenyl ring of aminophosphino moiety, showed the highest enantioselectivity. [ABSTRACT FROM AUTHOR]

A new class of sterically hindered chiral ferrocenyl P,N,N-ligands have been prepared through a two-step transformation from (Sc,Rp)-PPFNH2, in which a new (R)-stereogenic center at the pyridinylmethyl position was generated in high diastereoselectivity. With these newly developed P,N,N-ligands, Ir-catalyzed asymmetric hydrogenation of various α-alkyl-substituted β-aryl-β-ketoesters via dynamic kinetic resolution has been realized in high diastereo- and enantioselectivities for the first time, which led to a variety of optically active anti-β-hydroxyesters in up to 99% ee. The study indicated that the additional stereocenter at the pyridinylmethyl position of these ligands is crucial to realize this hydrogenation. [ABSTRACT FROM AUTHOR]

A new family of chiral ferrocenyl P,S-ligands has been developed and successfully applied in a highly endo-selective catalytic asymmetric cycloaddition of azomethine ylides with various enones, including cyclic and acyclic α-enones. For cyclic α-enones, a [Cu(CH3CN)4]ClO4/(Rc,SFc)-2fcomplex catalyzed the cycloaddition to give the sole endo-cycloadducts in perfect enantioselectivities (normally 99% ee), while an AgOAc/(Rc,SFc)-2fcatalytic system exhibited good endo/exoselectivities (endo/exo= 91/9 to 96/4) and high enantiocontrol (up to 98% ee) for acyclic α-enones. [ABSTRACT FROM AUTHOR]

A new class of unsymmetrical hybrid phosphine-aminophosphine ligands has been prepared from commercially available, inexpensive (S)-1-phenylethylamine through a concise synthetic procedure. These ligands are not very sensitive to air and moisture, and displayed good enantioselectivities in the Rh-catalyzed asymmetric hydrogenation of various dimethyl α-benzoyloxyethenephosphonates bearing β-aryl, β-alkyl, and β-alkoxy substituents and N-benzyloxycarbonyl α-enamido phosphonates, in which up to 97% ee was obtained. A side-by-side comparison study disclosed that these new phosphine-aminophosphine ligands showed better enantioselectivity than BoPhoz ligands. [ABSTRACT FROM AUTHOR]

The first copper-catalyzed asymmetric formal [4 + 2] cycloaddition of o-aminophenol derivatives with propargylic esters as the bis-electrophilic C2 synthons for the stereoselective construction of chiral 2,3,4-trisubstituted 2H-1,4-benzoxazines bearing an exocyclic double bond has been developed. By using a structurally modified chiral ketimine P,N,N-ligand, a wide range of optically active 2H-1,4-benzoxazines were prepared in high yields and with excellent enantioselectivities (up to 97% ee). [ABSTRACT FROM AUTHOR]

Terminal propargylic compounds containing an alkyne unit and an alcohol or ester group in the propargylic position have a fairly acidic acetylenic hydrogen atom; this makes them versatile substrates for further chemical transformation. Some transition metals such as ruthenium or copper exhibit specific affinity for terminal propargylic compounds, generating dielectrophilic ruthenium- or copper-allenylidene complexes that show high potential for stereoselective cycloaddition with various bis-nucleophiles. In this review, we highlight this emerging field of catalytic stereoselective cycloaddition with terminal propargylic compounds. Examples of ruthenium-, copper-, palladium-, and goldcatalyzed cycloaddition are given in the article, along with mechanistic considerations. 1 Introduction 2 Ruthenium-Allenylidene Complexes in Enantioselective Cycloaddition 3 Copper-Allenylidene Complexes in Enantioselective Cycloaddition 4 Palladium-p-Propargyl Complexes in Stereoselective Cycloaddition 5 Gold-Carbenoid Complexes in Stereoselective Cycloaddition 6 Summary and Outlook [ABSTRACT FROM AUTHOR]

The first highly diastereo- and enantioselective propargylic alkylation of acyclic ketone enamines to form vicinal tertiary stereocenters has been reported by employing copper catalysis in combination with a bulky and structurally rigid tridentate ketimine P,N,N-ligand. [ABSTRACT FROM AUTHOR]

A new Cu-catalyzed asymmetric [3 + 3] cycloaddition of propargyl esters with cyclic enamines is reported. With a combmatiori of Cu(OAc)2∙H2O and a chiral tridentate ferrocenyl-P,N,N ligand as the catalyst, perfect endo selectivities (endo/exo > 98/2) and excellent enantioselectivities (up to 98% ee) for endo cycloadducts were achieved under mild conditions. This method provides a simple and efficient approach for the synthesis of optically active bicyclo[n.3.1] frameworks. [ABSTRACT FROM AUTHOR]

A series of chiral -aryl--amino acid ester derivatives were synthesized in high enantioselectivities (93−97% ee) via the Rh-catalyzed asymmetric hydrogenation of -phthalimido-,-unsaturated carboxylic acid esters using highly modular chiral BoPhoz-type phosphine−aminophosphine ligands. The method has been applied successfully to the synthesis of several chiral pharmaceuticals including (R)-baclofen and (R)-rolipram with high enantioselectivities. [ABSTRACT FROM AUTHOR]