Catalytic enantioselective transamination of alpha-keto esters: an organic approach to enzymatic reactions

The half-transamination reaction of alpha-keto esters with pyridoxamine or 4-picolylamine was found to be catalysed by different metal catalysts in organic solvents giving moderate yields and enantioselectivities of up to 37% ee for methyl-3-indole pyruvate.     

Strong Electronic Effects in the cis‐Selective Asymmetric Cyclopropanation of Olefins Catalyzed by [RuCl(PNNP)]+

The cationic [RuCl(PNNP)]⁺ catalysts containing tetradentate ligands with a P₂N₂ donor set (PNNP) show strong electronic effects in the cyclopropanation of para‐substituted styrenes. The reactivity trend confirms that the carbene transfer to the olefin has electrophilic character. Linear free‐energy relationships are observed for the relative reactivity, the cis/trans selectivity, and for the enantioselectivity (of the cis‐cyclopropane). The linear correlation between log (k_X/k_H) and σ shows a large value of ρ (−2.4), which is indicative of significant charge buildup in the transition state of the carbene transfer to the olefin. All the relevant parameters (reactivity, diastereoselectivity, and enantioselectivity) increase with the increasing electron density at the C=C bond. To define the scope of the [RuCl(PNNP)]⁺ catalysts, 1‐ and 2‐substituted styrenes, and oct‐1‐ene were also investigated.     

First observation of the decays B(0) → D(+)K(-)π(+)π(-) and B(-) → D(0)K(-)π(+)π(-)

First observations of the Cabibbo-suppressed decays B(0) → D(+)K(-)π(+)π(-) and B(-) → D(0)K(-)π(+)π(-) are reported using 35 pb(-1) of data collected with the LHCb detector. Their branching fractions are measured with respect to the corresponding Cabibbo-favored decays, from which we obtain B(B(0) → D(+)K(-)π(+)π(-))/B(B(0) → D(+)π(-)π(+)π(-))=(5.9±1.1±0.5)×10(-2) and B(B(-) → D(0)K(-)π(+)π(-))/B(B(-) → D(0)π(-)π(+)π(-))=(9.4±1.3±0.9)×10(-2), where the uncertainties are statistical and systematic, respectively. The B(-) → D(0)K(-)π(+)π(-) decay is particularly interesting, as it can be used in a similar way to B(-) → D(0)K(-) to measure the Cabibbo-Kobayashi-Maskawa phase γ.     

Differential branching fraction and angular analysis of the decay B0 → K*0 μ+ μ-

The angular distributions and the partial branching fraction of the decay B0 → K*0 μ+ μ- are studied by using an integrated luminosity of 0.37 fb(-1) of data collected with the LHCb detector. The forward-backward asymmetry of the muons, A(FB), the fraction of longitudinal polarization, F(L), and the partial branching fraction dB/dq2 are determined as a function of the dimuon invariant mass. The measurements are in good agreement with the standard model predictions and are the most precise to date. In the dimuon invariant mass squared range 1.00-6.00 GeV2/c4, the results are A(FB)=-0.06(-0.14)(+0.13)±0.04, F(L)=0.55±0.10±0.03, and dB/dq2=(0.42±0.06±0.03)×10(-7) c4/GeV2. In each case, the first error is statistical and the second systematic.     

Radical Anions of Polyalkylazulenes: An ESR and ENDOR Study

Proton-hyperfine data are reported for the radical anions generated from azulene ( 1 ) and its alkyl derivatives 2 – 11 in 1,2-dimethoxyethane both ‘chemically’ with K and electrolytically. The alkyl derivatives are 1,3-dimethyl- ( 2 ), 5,7-dimethyl- ( 3 ), 1,3,5,7-tetramethyl- ( 4 ), 2-methyl- ( 5 ), 4,6,8-trimethyl- ( 6 ), 2,4,6,8-tetramethyl-( 7 ), 1,3,4,6,8-pentamethyl- ( 8 ), 1,3,4,8-tetramethyl-6-propyl- ( 9 ), 6-(tert-butyl)-1,3,4,8-tetramethyl- ( 10 ), and 1,2,3,4,6,8-hexamethylazulene ( 11 ). Alkyl substituents at the odd-numbered centers μ = 1, 3, 5, and 7 partly shift the π-spin population from the seven- to the five-membered ring, whereas those at the even-numbered centers μ = 4, 6, and 8 exert an opposite effect on the π-spin distribution.     

OptiDose: Computing the Individualized Optimal Drug Dosing Regimen Using Optimal Control

Journal of Optimization Theory and Applications - Providing the optimal dosing strategy of a drug for an individual patient is an important task in pharmaceutical sciences and daily clinical...