The combination of 0 valent palladium precursor and bromo-substituted 1,3-diaryl-imidazoline carbene ligand precursor such as 1-(2-bromophenyl)-3-(2,6-diisopropylphenyl)-imidazolinium chloride 1a exhibited high catalytic activity for the 1,2-addition of arylboronic acids to aldehydes including aqueous formaldehyde.

Ru(II)–xantphos catalysis is found to be effective for the addition reaction of 2-phenylbenzoic acid onto unactivated olefins. Thus, the reactions of 2-phenylbenzoic acid and unactivated olefins are carried out in the presence of 5 mol % of Ru(II)–xantphos catalysis in refluxing CHCl3 for 48 h to afford the corresponding esters in 40–95% yield. The control experiments indicate that the influence of TfOH for Brønsted acid catalyst was vanishingly small in our new catalytic system.Xantphos showed high catalytic activity. Thus, Ru-catalyzed addition reaction of 2-phenylbenzoic acid with unactivated olefins using xantphos as a ligand provided the corresponding esters in good to excellent yields.

A combination of palladium with ferrocene-based phosphine ligand with a carbon–bromine bond was found to be a good catalyst for the 1,4-addition of arylboronic acids to α,β-unsaturated ketones and the 1,2-addition to aldehydes. Using Pd(dba)2 and (S,Rp)-[1-(2-bromoferrocenyl)ethyl]diphenylphosphine (S,Rp)-1, 3-phenylcyclohexanone was obtained from the reaction of 2-cyclohexen-1-one with phenylboronic acid in the presence of K2CO3 in toluene at room temperature after 3 h in 92% yield with 76% ee. In the 1,2-addition of 4-methylphenylboronic acid to benzaldehyde, 96% of (4-methylphenyl)phenylmethanol was afforded after 24 h, while the enantiomeric excess was only 6%.(S)-3-PhenylcyclohexanoneC12H14OEe = 76%[α]D25=-17.2 (c 1.05, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-3-(4-Methyphenyl)cyclohexenoneC13H16OEe = 78%[α]D25=-12.0 (c 1.00, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-3-(4-Methoxyphenyl)cyclohexenoneC13H16O2Ee = 76%[α]D25=-11.0 (c 1.05, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-3-(4-t-Butylphenyl)cyclohexanoneC16H22OEe = 79%[α]D25=-12.0 (c 1.00, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-3-(4-Trifluoromethylphenyl)cyclohexanoneC13H13F3OEe = 4%[α]D25=-1.0 (c 1.00, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-3-(4-Fluorophenyl)cyclohexanoneC12H13FOEe = 45%[α]D25=-17.7 (c 0.51, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-3-(1-Naphthyl)cyclohexanoneC16H16OEe = 42%[α]D25=-39.0 (c 1.00, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-3-PhenylcyclopentanoneC11H12OEe = 54%[α]D25=-45.5 (c 1.01, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-3-PhenylcycloheptanoneC13H16OEe = 38%[α]D25=-28.2 (c 1.10, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-4-Phenyl-2-pentanoneC11H14OEe = 44%[α]D25=+14.0 (c 0.50, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-5-Phenyl-3-hexanoneC12H16OEe = 47%[α]D25=+26.0 (c 0.50, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-5-Methyl-4-phenyl-2-hexanoneC13H18OEe = 52%[α]D25=-16.0 (c 0.50, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-4-Phenyl-2-nonanoneC15H22OEe = 42%[α]D25=20.0 (c 0.50, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

The kinetic resolution of racemic 2-isoxazolines was carried out by asymmetric reduction using borane with 1,2-amino alcohols as a chiral source. Using excess BH3–THF in the presence of (−)-norephedrine, optically active 1,3-amino alcohol derivatives were obtained with good ee but in lower yield, while the optically active substrates 2-isoxazolines were recovered with modest ee. The asymmetric reduction using 2.0 equiv of BH3–SMe2 was investigated as an alternative strategy for the synthesis of optically active products. After reduction, treatment of the resulting mixture with Et3N was successful in providing optically active isoxazolidine derivatives in good yields and with good ee. The choice of chiral source was also shown to have a significant effect. In particular, the use of (S)-α,α-diphenyl-2-pyrrolidinemethanol reversed the enantioselectivity of the recovered substrates.(S)-3,5-Diphenyl-2-isoxazolineC15H13NOEe = 21%[α]D20=+52.1 (c 3.245, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(4S,5S)-3,r-4,t-5-Triphenyl-2-isoxazolineC21H17NOEe = 7%[α]D20=+34.8 (c 4.855, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (4S,5S)(S)-3,5-Diphenyl-5-methyl-2-isoxazolineC16H15NOEe = 17%[α]D20=+10.0 (c 5.51, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-5-(2-Naphthyl)-3-phenyl-2-isoxazolineC19H15NOEe = 15%[α]D20=+40.3 (c 4.07, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-3-(4-Nitrophenyl)-5-phenyl-2-isoxazolineC15H12N2O3Ee = 13%[α]D20=+36.1 (c 2.935, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(1R,3S)-3-Benzoylamino-1,3-diphenyl-1-propanolC22H21NO2Ee = 74%[α]D20=+21.15 (c 1.655, acetone)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,3S)(1S,3S)-3-Benzoylamino-1,3-diphenyl-1-propanolC22H21NO2Ee = 81%[α]D20=-13.0 (c 1.15, acetone)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,3S)(1R,3S)-1,3-Diphenyl-3-tosylamino-1-propanolC22H23NO3SEe = 68%[α]D20=-13.5 (c 2.445, acetone)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,3S)(1S,3S)-1,3-Diphenyl-3-tosylamino-1-propanolC22H23NO3SEe = 78%[α]D20=-137.3 (c 0.59, acetone)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,3S)(3S,5R)-N-Benzoyl-3,5-diphenylisoxazolidineC22H19NO2Ee = 65%[α]D20=-4.5 (c 7.08, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S,5R)(3S,5S)-N-Benzoyl-3,5-diphenylisoxazolidineC22H19NO2Ee = 74%[α]D20=-80.23 (c 3.95, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S,5S)(3S,5R)-N-Benzoyl-3-(4-nitrophenyl)-5-phenylisoxazolidineC22H18N2O4Ee = 70%[α]D20=+5.8 (c 4.83, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S,5R)(3S,5S)-N-Benzoyl-3-(4-nitrophenyl)-5-phenylisoxazolidineC22H18N2O4Ee = 71%[α]D20=-60.2 (c 1.795, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S,5S)(3S,4R,5R)-N-Benzoyl-3,4,5-triphenylisoxazolidineC28H23NO2Ee = 76%[α]D20=-5.3 (c 4.535, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S,4R,5R)(3S,4S,5S)-N-Benzoyl-3,4,5-triphenylisoxazolidineC28H23NO2Ee = 71%[α]D20=+86.9 (c 3.705, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S,4S,5S)(3S,5R)-N-Benzoyl-3,5-diphenyl-5-methylisoxazolidineC23H21NO2Ee = 58%[α]D20=-5.3 (c 4.375, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S,5R)(3S,5S)-N-Benzoyl-3,5-diphenyl-5-methylisoxazolidineC23H21NO2Ee = 60%[α]D20=-75.0 (c 1.92, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S,5S)(3S,5R)-N-Benzoyl-5-(2-naphthyl)-3-phenylisoxazolidineC26H21NO2Ee = 66%[α]D20=+21.4 (c 3.555, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S,5R)

The asymmetric amination of aryl halides with racemic amines was examined in the presence of a transition metal complex having a chiral ligand. The yield and enantioselectivity of the products were strongly influenced by the kind of base, reaction temperature, solvent, and the additive. The best result was obtained from the reaction of 2-iodoanisole with 1-(1-naphthyl)ethylamine in the presence of sodium methoxide and 18-crown-6 by Pd–Tol–BINAP to afford the product in 70% yield with 80% ee.(S)-4-Phenyl-N-(1-phenylethyl)anilineC20H19NEe = 21%[α]D25=-11.9 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-4-Methyl-N-(1-phenylethyl)anilineC15H17NEe = 20%[α]D25=+26 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-3-Methyl-N-(1-phenylethyl)anilineC15H17NEe = 16%[α]D25=+16 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-2-Methyl-N-(1-phenylethyl)anilineC15H17NEe = 25%[α]D25=+14 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(R)-4-Methoxy-N-(1-phenylethyl)anilineC15H17NOEe = 21%[α]D25=+6.0 (c 0.3, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)(R)-3-Methoxy-N-(1-phenylethyl)anilineC15H17NOEe = 19%[α]D25=+8.0 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)(S)-2-Methoxy-N-(1-phenylethyl)anilineC15H17NOEe = 30%[α]D25=+14.0(c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-N-(1-(1-Naphthyl)ethyl)-4-phenylanilineC24H21NEe = 37%[α]D25=+86 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(R)-2-Methyl-N-(1-(1-naphthyl)ethyl)anilineC19H19NEe = 100%[α]D25=+226 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)(R)-N-(1-(1-Naphthyl)ethyl)anilineC18H17NEe = 75%[α]D25=+142 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)(S)-2-Methoxy-N-(1-(1-naphthyl)ethyl)anilineC19H19NEe = 80%[α]D25=+170 (c 0.3, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

The cationic ruthenium catalyst (Cp*RuCl2)2/AgOTf/Ligand promotes the addition reaction of carboxylic acids across olefins without β-hydride elimination.

Reductions of acetals to ethers and of orthoester to acetal by hydrosilane using rhodium catalyst are described.

New BINOL-derived ligands, 3,3′-bis(2-oxazolyl)-1,1′-bi-2-naphthols (BINOL-Box), bearing chiral bis-oxazoline at the 3,3′-carbons, were synthesized from commercially available 1,1′-bi-2-naphthol (BINOL). With the new ligands obtained, we found that asymmetric 1,3-dipolar cycloaddition reaction of N-benzylidenebenzylamine N-oxide (2) to 3-((E)-2-butenoyl)-1,3-oxazolidin-2-one (1) was catalyzed by BINOL-Box–scandium complexes to give isoxazolidine 3 in high yield with high diastereo- and enantioselectivity. For example, the reaction of 1 with 2 catalyzed by a 6 mol% (S,R)-7d and 5 mol% Sc(OTf)3 complex proceeded to give the endo-3 as the major diastereomer with an endo:exo ratio of 97:3 and 87% ee of the endo-product in the presence of 4 Å molecular sieves. Interestingly, the absolute configuration of the major product was changed according to the kind of additive used.