Jeanine Blumenfeld

Structural requirements in chiral diphosphine-rhodium complexes: III. Small scale method for fresh preparation of cationic diop-rhodium complexes and comparison with neutral diop-rhodium complexes

Abstract (—)-2,3-Isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP) was used in cationic rhodium(I)-diphosphine complexes, freshly prepared on a milligram scale, to catalyze the asymmetric hydrogenation of ( Z )-α-acetamidocinnamic acid. These cationic complexes were found not to be air stable over a period of time, but when utilized after storage under argon reproducible kinetic results were noted, and the optical purity of the reduction product was found to be independent of the age of the cationic complex. The cationic rhodium(I)DIOP complex was found to be a more reactive complex than the corresponding neutral chlororhodium(I)-DIOP complex when used in asymmetric hydrogenations, but both gave the same optical yield.

STRUCTURAL REQUIREMENTS IN CHIRAL DIPHOSPHINE-RHODIUM COMPLEXES. XI. ASYMMETRIC HOMOGENEOUS HYDROGENATION OF Z-α-ACYLAMINOCINNAMIC ACIDS AND ESTERS WITH (1S,2S)-TRANS-1,2-BIS(DIPHENYLPHOSPHINOMETHYL)CYCLOHEXANE/RHODIUM(I) COMPLEXES

Z-α-acylaminocinnamate esters were hydrogenated with neutral rhodium(I) complexes containing (1S, 2S)-trans-1,2-bis(diphenylphosphinomethyl)cyclohexane. Increasing the steric bulk of the alcohol moiety of the ester function results in increased enantioface differentiation in favor of the re-si prochiral face to yield an excess of the S-amino acid derivatives. In the series of N-acetylphenylalanine ester products (resulting from hydrogenation of Z-α-acetamidocinnamate esters) the optical purity increased from 1% ee-(R) [Me]; 20% ee-(S) [Et]; 47% ee-(S) [i-Pr]; to 58% ee-(S) [t-Bu]. Increasing the steric bulk of the acyl function (NHCOR, where R is an alkyl moiety) favors the reduction of the si-re prochiral face [in the methyl ester substrates] to yield an excess of the R-amino acid derivatives. In the series of N-acylphenylalanine methyl ester products (resulting from hydrogenation of Z-methyl α-acylaminocinnamates) the optical purity increased from 1% ee-(R) [Me]; 13% ee-(R) [i-Pr]; to 15% ee-(R) [t-Bu and 1-adamantyl]. The α-formamido and α-benzamido substrates gave hydrogenation products having 22% ee-(R) [H] and 35% ee-(R) [Ph]. In the corresponding free acids, increasing the steric bulk of the acyl function (NHCOR, where R is an alkyl moiety) results in almost no change in the optical purity of the reduction products. In the series of N-acylphenyl-alanine products (resulting from hydrogenation of Z-α-acylaminocinnamic acids) the optical purity was 35% ee-(S) [Me]; 31% ee-(S) [i-Pr]; 33% ee-(S) [t-Bu]; and 35% ee-(S) [1-adamantyl]. The α-benzamido substrate gave a hydrogenation product having 8% ee-(S).

Fatty acid composition of breastmilk of Israeli mothers

We conducted this study to determine the fatty acid composition of breastmilk of Israeli women and compare it with baby milk substitutes. Samples of mature breast milk, from 29 lactating Israeli Jewish mothers were collected during feedings. Total milk lipids extracts were transmethylated and analyzed by using an improved gas-chromatographic method. About 72% of the total fatty acids in the investigated breast milk comprised oleic (18:1c; 31±4%), palmitic (16:0; 21±4%), and linoleic (18:2n-6; 20±4%) acids. Total saturated fatty acids represented 42±7% of total fatty acids. The monounsaturated fatty acids content was 33±5%, of which 94% was oleic acid, and the polyunsaturated fatty acids content was about 24±4%, of which 85% was linoleic acid. The α-linolenic acid level found in this study, 2.0±0.6%, was higher than the range of values reported for the world population (0.10–1.4%). The main fatty acids composition of the milk substitutes has very similar composition to the breast milk. Docosahexaenoic acid levels are particularly low among the population of Jewish nursing mothers in relation to the milk substitutes, containing docosahexaenoic acid in their formulations.

Structural requirements in chiral diphosphine-rhodium complexes. X1 asymmetric homogeneous hydrogenation of z-N-acetyldehydroamino acids and esters with (1R,2R)-trans-1,2-bis(diphenylphosphinomethyl)cyclobutane/rhodium(I) complexes.

Abstract Z-α-acetamidocinnamate esters were hydrogenated with neutral rhodium(I) complexes containing (1R,2R)-trans-1,2-bis(diphenylphosphinomethyl)cyclobutane. Increasing the steric bulk of the alcohol moiety in the unsaturated esters had little influence upon the optical purity of the N-acetylphanylalanine ester products. In the series Me, Et, i-Pr, and t-Bu the optical purity decreased from 44 % ee-(R) [Me] to 40 % ee-(R) [t-Bu]. The chiral cyclobutane diphosphine appears to be only slightly more effective than the heterocyclic DIOP when ring-substituted Z-α-acetamidocinnamic acids are hydrogenated with neutral rhodium(I) complexes without the addition of triethylamine. Addition of triethylamine to the solvent blend seems to be more beneficial to the cyclobutane analogue than to DIOP.

Role of Radicals in the Lipid Peroxidation Products of Commercial Infant Milk Formula

Four commercial brands of infant milk formula were investigated, and the amount of shelf lipid peroxidation was determined by measuring malondialdehyde (MDA) or, more exactly, thiobarbituric acid reactive substance (TBARS) levels, which are the end products of lipid peroxidation. TBARS level, indicated by MDA concentration, was higher in the vegetarian brands. The vegetarian brands are, as expected, more prone to oxidation than dairy brands, as they contain more unsaturated fats. The introduction of formate anion diminishes the peroxide amounts initially present in the milk samples as well as those induced by radiation-induced oxidation.

Structural requirements in chiral diphosphine-rhodium complexes. VIII. Asymmetric hydrogenation of N-acetyldehydroamino acids with rhodium(I) complexes containing chiral carbocyclic analogues of DIOP.

Abstract Z-α-acetamidocinnamic acid was hydrogenated with neutral diphosphine-rhodium(I) complexes containing trans-1,2-bis(diphenylphosphinomethyl) cycloalkanes to give N-acetylphenylalanine: 86 % e.e.-(R) [(1R,2R)-cyclobutane]; 63 % e.e.-(R) [(1R,2R)-cyclopentane]; 35 % e.e.-(S) [(1S,2S)-cyclohexane]; and 82 % e.e.-(R) [(2R,3R)-DIOP]. Similarly, α-acetamidoacrylic acid was hydrogenated to give N-acetylalanine: 72 % e.e.-(R) [(1R,2R)-cyclobutane]; 72 % e.e.-(R) [(1R,2R)-cyclopentane]; 40 % e.e.-(S) [(1S,2S)-cyclohexane]; and 73 % e.e.-(R) [(2R,3R)-DIOP].

Structural requirements in chiral diphosphine-rhodium complexes. VI. Inhibition of the asymmetric hydrogenation of Z-methyl-α-acetamidocinnamate catalyed by diop-rhodium catalyst in the presence of Z-adamantyl or bornyl-α-acetamidocinnamate.

Abstract The half-life period (6.6 mm.) for the hydrogenation of Z-methyl-a-acetamidocinnamate (catalyzed by a neutral DIOPRh complex) was found to be the same when the Me ester reduction was performed in the presence of equimolar quantities of the corresponding i-Pr or t-Bu ester unsaturated stbstrates. Neither the Me nor the i-Pr or t-Bu esters underwent appreciable Z,E-isomerization. The formation of N-acetylphenylalanine methyl ester product suffered inhibition when the hydrogenation reaction was performed in the presence of the corresponding bornyl or 1-adamantyl unsaturated esters (half-life period of the Me ester: 27 ~ 40 mm., respectively. The greater the inhibition of the Me ester unsaturated substrate, the more the bulky inhibitor itself underwent Z,E-isomerization. In the presence of inhibitors, the Me unsaturated substrate did not undergo appreciable Z,E-isomerization.

Role of lycopene in preventing lipid peroxidation products, in commercial infant milk formula

Abstract Objectives: The aim of the study was to investigate whether lycopene from natural sources (tomato extract) is able to protect newborns milk formula, against oxidative damage caused by exposure to hydroxyl radicals, and is there a difference between milk substitutes from various sources. Methods: Four commercial brands of infant milk formula: two of the formulas were dairy milk (A-d and B-d) and two were based on soy bean vegan milk (A-s and B-s), were exposed to ionizing radiation radical (·OH). Lipid peroxidation was determined by measuring malondialdehyde (MDA) using thiobarbituric acid reactive substance test (TBARS). Results: When suspensions containing the four brands of formula were subjected to oxidizing media produced by ionizing radiation (hydroxyl radicals), lipid peroxidation increased linearly as a function of the irradiation dose (R = 0.99). It was found that lycopene in a concentration of 0.6 mM, reduced the radiation damage only in the soy-based formula; decrease of ∼40% of the damage achieved in B-s, and ∼20% reduction in the damage caused to A-s, significantly p < 0.01. Conclusions: Lycopene in dairy milk did not protect against hydroxyl radicals; however, lycopene found to protect against hydroxyl radicals in soy milk. This result suggests different mechanisms of radical production that arises from high iron levels present in the soy milk and involving the high-valent iron peroxo species.