Titanium(IV)-catalyzed enantioselective sulfenylation of beta-ketoesters

A [Ti(TADDOLato)] complex (1) catalyzes the enantioselective sulfenylation of beta-ketoesters using phenylsulfenyl chloride, giving ees of up to 88% and yields of up to 95%. The reaction does not require the presence of a base. [reaction: see text]     

Lewis base activation of Lewis acids: catalytic, enantioselective vinylogous aldol addition reactions

The generality of Lewis base catalyzed, Lewis acid mediated, enantioselective vinylogous aldol addition reactions has been investigated. The combination of silicon tetrachloride and chiral phosphoramides is a competent catalyst for highly selective additions of a variety of alpha,beta-unsaturated ketone-, 1,3-diketone-, and alpha,beta-unsaturated amide-derived dienolates to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded high enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although alpha,beta-unsaturated ketone-derived dienolate did not react with aliphatic aldehydes, alpha,beta-unsaturated amide-derived dienolates underwent addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivities achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride-chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated.     

Anionic ligand exchange on ZrPO(4)Cl(dmso): alkoxide and carboxylate derivatives

This paper reports the preparation and characterization of a series of organic derivatives of ZrPO(4)Cl(CH(3))(2)SO obtained by topotactic anion exchange of chloride ligands with several n-alkoxide (RO) and carboxylate groups (RCOO). Exchange with alkoxides, with an alkyl chain length from 2 to 8 carbon atoms, gave products of general formula ZrPO(4)RO(CH(3))(2)SO. In these derivatives alkoxide groups, covalently bonded to zirconium atoms via Zr-O bonds, point toward the interlayer region. Carboxylate derivatives, of general formula ZrPO(4)[(RCOO)(CH(3))(2)SO](1)(-)(x)(OH H(2)O)(x), were obtained using benzoate (x = 0), nitrobenzoate (x = 0.3), and phenylacetate (x = 0.2) groups. The thermal behavior of these organic derivatives is discussed. Due to this reactivity, ZrPO(4)Cl(CH(3))(2)SO is an attractive precursor for materials chemistry.     

Synthesis of aryl(ferrocenyl)methanols via an enantioselective addition of arylboronic acids

Enantiomerically enriched ferrocenyl alcohols are important intermediates in the synthesis of a range of chiral ferrocene-derived ligands. We studied various possibilities for their synthesis by the catalytic enantioselective addition of arylboronic acids to ferrocenyl carbonyl compounds. The best system comprised of ferrocenyl oxazolinyl alcohol as a catalyst and an arylation reagent generated from a boronic acid and diethylzinc. Aryl ferrocenyl methanols were synthesized in yields of up to 97% and with enantiomeric purities of up to er 98:2.     

Diastereo- and enantioselective aldol reaction of granatanone (pseudopelletierine)

Granatanone (granatan-3-one, 9-methyl-9-azabicyclo[3.3.1]nonan-3-one, pseudopelletierine or pseudopelletrierin) undergoes deprotonation with lithium amides giving a lithium enolate, which reacts with aldehydes diastereoselectively giving exclusively exo isomers and anti/syn selectivity up to 98:2. Granatanone can be enantioselectively lithiated by chiral lithium amides and the resulting non-racemic enolate can be reacted with aldehydes giving aldols with enantiomeric excess up to 93% (99% ee after recrystallization). The absolute and relative configuration of the aldol products was determined by NMR spectroscopy and X-ray analysis.Granatanone; aldol reaction; asymmetric synthesis; enantioselective deprotonation; chiral lithium amide.     

"Oxidative addition" to a Zirconium(IV) redox-active ligand complex

A strategy to enable reactivity analogous to oxidative addition is presented for d(0) transition-metal complexes. The reaction of the redox-active ligand 2,4-di-tert-butyl-6-tert-butylamidophenolate (ap) with ZrCl(4)(THF)(2) affords the new complex Zr(IV)(ap)(2)(THF)(2). This compound is formally zirconium(IV) and contains no d electrons; however, exposure of Zr(IV)(ap)(2)(THF)(2) to chlorine gas results in swift chlorine addition at the zirconium metal center via one-electron oxidation of each ap ligand. The diradical product, Zr(IV)Cl(2)(isq)(2) (isq = 2,4-di-tert-butyl-6-tert-butyliminosemiquinone), has been characterized by X-ray crystallography, electron paramagnetic resonance spectroscopy, and SQUID magnetometery.     

Separation of amines by ligand exchange: Part IV ligand exchange with chelating resins and cellulosic exchangers

Chelating, sulfonic and cellulosic exchangers were compared in ligand exchange chromatography. Chelating resins retain metal ions the best, but have a low ligand binding capacity. Cellulosic exchangers show excessive metal leakage. Sulfonated polystyrene resins loaded with nickel ions give best results in most cases. Data are presented on ligand exchange chromatography of simple aliphatic amines, hydrazine and substituted hydrazines, purine and pyrimidine bases.     

Aminohydroxyphosphine ligand for the copper-catalyzed enantioselective conjugate addition of organozinc reagents

An alanine-derived aminohydroxyphosphine ligand was developed for copper-catalyzed asymmetric conjugate addition of organozinc reagents to alpha,beta-unsaturated carbonyl compounds. This new tridentate ligand induces consistently high enantioselectivity in reactions of a variety of acyclic substrates. Theoretical mechanistic analysis suggests that the C-C bond formation takes place through a highly ordered transition state by the coordination of the phosphorus and nitrogen atoms to the copper(III) and zinc(II) atoms, respectively, and of the oxygen anion to both the metal centers.     

An aldol approach to the enantioselective synthesis of (-)-oseltamivir phosphate

A formal asymmetric synthesis of the antiviral agent (-)-oseltamivir phosphate is achieved using two aldol reactions as key steps.     

C(2)-symmetric Sc(III)-complexes as chiral Lewis acids. Catalytic enantioselective aldol additions to glyoxylate esters

Cationic Lewis acid complexes [Sc(pyridyl-bis(oxazolinyl)](Cl(2))SbF(6) 1a and 1b catalyze aldol reactions with ethyl glyoxylate with enantioselectivities ranging from 90 to 99% ee and syn reaction diastereoselections ranging from 90:10 to 95:5. [reaction: see text]     

New (S)-proline derivatives as catalysts for the enantioselective aldol reaction

(2S)-N- 2-[(R)-Hydroxy(phenyl)methyl]phenylpyrrolidine-2-carboxamide, (2 S)-N-{2-[(S)-hydroxy(phenyl)methyl]phenyl}pyrrolidine-2-carboxamide, and (S)-N-{2-[hydroxy-(diphenyl)methyl]phenyl}pyrrolidine-2-carboxamide were obtained and tested as catalysts for an asymmetric aldol reaction of 4-nitrobenzaldehyde with acetone.     

A tetrameric copper(I) alkoxide with a π-tethered ligand: 2-allyl-6-methylphenoxocopper(I)

The complex 2-allyl-6-methylphenoxocopper(I) has been prepared by reaction between mesitylcopper(I) and 2-allyl-6-methylphenol. Crystallographic studies show that the compound is tetrameric with a distorted cubane-type copper(I)-oxygen core, and with additional π-coordination of the ligand to copper through the alkene functionality (ν(CC)=1520 cm⁻¹). The ligands thus act both as chelates and as bridges between adjacent copper(I) centres. Copper(I) exhibits trigonal pyramidal coordination geometry with CuC distances to the CC group of 1.976(9) and 2.017(11) Å and CuO distances of 1.973(6), 2.021(6) and 2.577(6) Å, respectively.     

Application of the chiral bis(phosphine) monoxide ligand to catalytic enantioselective addition of dialkylzinc reagents to beta-nitroalkenes

[reaction: see text] Me-DuPHOS monoxide is shown to be a very effective ligand in the enantioselective copper-catalyzed addition of dialkylzinc reagents to beta-nitroalkenes providing access to chiral nitroalkanes. The major advantages of this process are high yields, broad and complementary substrate scope, and high enantioselectivities. The effect of achiral dummy ligands as an additive has also been documented.     

Cu(I)-catalyzed reductive aldol cyclizations: diastereo- and enantioselective synthesis of beta-hydroxylactones

[reaction: see text] Copper bisphosphine complexes catalyze the intramolecular reductive aldol reaction of alpha,beta-unsaturated esters with ketones, affording five- and six-membered beta-hydroxylactones in high stereoselectivities. Utilization of chiral nonracemic bisphosphines render the cyclizations enantioselective.     

Dinitrogen binding at vanadium in a tris(alkoxide) ligand environment

We report the first tris(alkoxide)V(III) complex to bind dinitrogen. Removal of THF from V(OR)(3)THF furnishes the highly reactive V(OR)(3) fragment, which binds dinitrogen to form [V(OR)(3)](2)(μ-N(2)) in the solid state. Dinitrogen is readily released upon dissolution of the complex. Structural and DFT studies are consistent with significant activation of N(2) when bound by the vanadium tris(alkoxide) platform.     

Imido Derivatives of Titanium (IV)

Reactions of titanium(IV) isopropoxide with acetamide, benzamide, and nicotinamide in different stoichiometric ratios in anhydrous benzene yielded imido derivatives of type (PrⁱO)_4-nTi(NHOCR)_n where n = 1, 2, 3, and 4; R = CH₃, C₆H₅, and C₅H₄N. All these complexes are insoluble in common organic solvents suggesting their polymeric nature. All these derivatives, with the exception of three which have characteristic melting points, did not sublime at 250°C in vacuo nor did they appear to decompose appreciably below 300°C. I.R. spectra of these derivatives are discussed.     

Chiral Palladium(II)-catalyzed asymmetric glyoxylate-Ene reaction: alternative approach to the enantioselective synthesis of alpha-hydroxy esters

An effective chiral palladium catalyst [Pd(CH(3)CN)(2)(S)-Tol-BINAP](SbF(6))(2) (2b) is developed for asymmetric glyoxylate-ene reactions. This palladium dicationic catalyst provides a simple but efficient approach to the asymmetric synthesis of alpha-hydroxy esters in excellent yields with high enantioselectivities at relatively higher reaction temperature (60 degrees C).