Synthesis and determination of maximum rotatory power of (+)-(S)-5-s-butyl-2(1H)-pyridinone

Optically active (S)-5-s-butyl-2(1H)-pyridinone ( 6 ) is obtained by reaction of 2-s-butylacrolein ( 1 ) and N-(carbamylmethyl)pyridinium chloride. The relationship between optical activity and minimum optical purity is determined.     

Optically active heteroaromatic compounds IX. Preparation,absolute configuration and optical purity of some chiral 3-alkylindoles

The Fischer and Brunner reactions as well as the Grignard alkylation of isatin have been used to prepare (S)-3-sec-butyl- and (S)-3-(2-methylbutyl)indoles, respectively, starting from (S)-1-chloro-2-methylbutane. The stereospecificity of the synthetic sequences followed has been investigated and the stereochemical relationships of the title compounds have been established.     

Synthesis of(+)-(2S, 6S)-trans-α-Irone and of(-)-(2S, 6S)-trans-γ-Irone

A 3:1 mixture of (+)-(2S, 6S)-trans-α-irone ((+)-1) and (?)-(2S, 6S)-trans-γ-irone (?)-2) has been synthesized with ca. 70% e. e. by the ene reaction of (?)-(S)-3 and but-3-yn-2-one.     

Markierte Vertreter eines möglichen Zwischenprodukts der Biosynthese von Fosfomycin inStreptomyces fradiae: Darstellung von (R,S)-(2-Hydroxypropyl)-, (R,S)-, (R)-, (S)-(2-Hydroxy-[1,1-2H2]propyl)-und (R,S)-(2-[18O]Hydroxypropyl)phosphonsäure

Summary Racemic methyl O-benzyllactate was reduced to the alcohol, transformed into the bromide and reacted with triethylphosphite to give the diethylphosphonate. Removal of protecting groups afforded a phosphonic acid which was purified as its cyclohexylammonium salt. (S)-Ethyl and (R)-isobutyl O-benzyllactate were reduced with LiAlD₄ to the corresponding dideuteriated alcohols, which were transformed in the same way as the racemic compound into the chiral (2-hydroxy-[1,1-²H₂]propyl)phosphonic acids. The optical purity of alcohols (S)- and (R)-6 b was determined by derivatisation with (+)-MTPA-Cl and¹H-NMR-spectroscopy to be 98%. Exchange of the carbonyl-16-oxygen atom of 2-oxopropylphosphonate for oxygen-18 from H₂ ¹⁸O, reduction with NaBH₄, deprotection and addition of cyclohexylamine yielded the salt (±)-18 of (2-[¹⁸O]hydroxypropyl)phosphonic acid.

     

Collagen cross-links: a convenient synthesis of tert-butyl-(2S)-2-[(tert-butoxycarbonyl)amino]-4-(2-oxiranyl)butanoate

An efficient synthesis of tert-butyl-(2S)-2-[(tert-butoxycarbonyl)amino]-4-(2-oxiranyl) butanoate (5), the key intermediate for preparation of collagen cross-links (+)-pyridinoline (Pyd, 1) and (+)-deoxypyridinoline (Dpd, 2) was described from (4S)-5-(tert-butoxy)-4-[(tert-butoxycarbonyl)amino]-5-oxopentanoic acid (6) in six steps. Also, an improved synthesis of iodide (2S)-(−)-4b was presented.     

Enantioselective Hydrogenation over Chiral Cobalt Complexes with (+)-(1S,2S,5R)-Neomenthyldiphenylphosphine and (-)-(R,R)-2,2-Dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolane

The optical yield in enantioselective hydrogenation of methyl -acetamidocinnamate over mono- and diphosphine cobalt(II) complexes CoX₂L₂ [where X = Cl or CF₃SO₃, L = (+)-(1S,2S,5R)-neomenthyl-diphenylphosphine or L2' = (-)-(R,R)-2,2-dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolane], which are generated in situ, in the presence of sodium tetrahydridoborate increases with rise in the phosphine-to-metal ratio and hydrogen pressure. The maximal optical yields of (+)-(S)-N-acetylphenylalanine methyl ester attain 40% (CoX₂L₂) and 42% (CoX₂L₂').     

Asymmetric Synthesis of (S)-4,5-Difluoro-2-Methylindoline

(S)-4,5-Difluoro-2-methylindoline (S)-11 was synthesized effectively by asymmetric reduction of N-[(R)-N-p-toIylsulfonyl]prolinyl-2-(2-oxo)propyl-3,4-difluoroanilide 4b followed by successive methylsulfonylation and intramolecular cyclization.     

A concise synthesis of (R)- and (S)-α-alkyl isoserines from d- and l-malic acids

A simple and diastereoselective method for the synthesis of (R)- and (S)-α-alkyl isoserines has been developed in four steps starting from commercially available d- and l-malic acid, respectively. This approach features stereocontrolled alkylation of 2-(2-tert-butyl-5-oxo-1,3-dioxolan-4-yl)acetic acid and proceeds through a methylcarbamate via a Curtius rearrangement.     

Synthesis of (5R)- and (5S)-5-Methyl-5, 6-dihydrouridine Derivatives

The hydrogenation of 2′, 3′-O-isopropylidene-5-methyluridine (1) in water over 5% Rh/Al₂O₃ gave (5 R)- and (5 S)-5-methyl-5, 6-dihydrouridine (2) , separated as 5′-O-(p-tolylsulfonyl)- (3) and 5′-O-benzoyl- (5) derivatives by preparative TLC. on silica gel and ether/hexane developments. The diastereoisomeric differentiation at the C(5) chiral centre depends upon the reaction media and the nature of the protecting group attached to the ribosyl moiety. The synthesis of iodo derivatives (5 R)- and (5 S)- 4 is also described. The diastereoisomers 4 were converted into (5 R)- and (5 S)-2′, 3′,-O-isopropylidene-5-methyl-2, 5′-anhydro-5, 6-dihydrouridine (7) .     

New Stereoselective GC Phases: Immobilized Chiral Polysiloxanes with (S)-(–)-t-Leucine Derivatives as Selectors

New chiral polysiloxanes have been prepared as stationary phases for gas chromatography, with (S)-(–)-t-leucine-t-butylamide, (S)-(–)-t-leucine-(S)-(–)-1-phenylethylamide, (S)-(–)-t-leucine-(S)-(–)-1-(α-naphthyl)ethylamide, (S)-(–)-t-leucine-(R)-( + )-1-phenylethylamide, and (S)-(–)-t-leucine-(R)-( + )-1-(α-naphthyl)ethylamide as selectors. Immobilization is achieved by radical-induced cross-linking with 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (V₄) and dicumyl peroxide (DCUP) as cross-linking reagents and cured at 170°C. Under these conditions, racemization of (S)-(–)-t-leucine is less than 4.5% (R) for 1 h curing, while for polysiloxanes with the conventional (S)-(–)-valine selectors about 20% of R-enantiomers are formed by racemization. In the presence of 5% (w/w) V₄ and 6% of DCUP with regard to the phases, 70–80% immobilization is achieved; without V₄, the degree of immobilization is about 50% for both the (S)-(–)-t-leucine and (S)-(–)-valine selectors. As the size of the amide moieties of the selectors increases from t-butyl to 1-(α-naphthyl)ethyl, the degree of immobilization decreases. If the curing time is prolonged to 2 h, the extent of racemization increases. The selectivity factors achieved for amino acid enantiomers and similar pharmaceuticals are generally higher than those obtained with the corresponding non-immobilized Chirasil-Val phases.     

SYNTHESIS OF (S,S)-BIS(4-ALKYLOXAZOLIN-2-YL-METHYL)-1,5-DIAZACYCLOOCTANE

ABSTRACT

Synthesis of a series of new chiral tetradentate ligands ((S,S)-1,5-bis(4-alkyloxazolin-2-yl-methyl)-1,5-diazacyclooctane) is described.     

6-氟-色满-2-羧酸的合成及其(R)-, (S)-光学异构体的拆分研究

以对氟苯酚为起始原料合成了6-氟-4-色满酮-2-羧酸, 该中间体经催化还原获得了消旋的6-氟-色满-2-羧酸. 化学拆分该消旋体和D-(＋)-α-苯乙胺及L-(－)-α-苯乙胺形成的非对映体盐, 分别得到了(R)-及(S)-6-氟-色满-2-羧酸.     

Infinite dilution activity coefficients and gas-to-liquid partition coefficients of organic solutes dissolved in 1-sec-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and in 1-tert-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Inverse gas chromatography was used to measure infinite dilution activity coefficients and gas-to-liquid partition coefficients for 48 organic solute probes in either 1-sec-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-tert-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide in the temperature range from 323.15 to 373.15 K. Partial molar excess enthalpies of solution were calculated from the variation of the infinite dilution activity coefficients with temperature. Abraham model correlations were also derived from the experimental partition coefficient data. The derived Abraham model correlations describe the observed partition coefficients to within 0.11 log units.     

Synthesis and Physical Properties of New Ferroelectric Liquid Crystals Consisting of 2(S)-[2 (S)-Methylbutyloxy] Propanol

New ferroelectric liquid crystals containing two chiral centers, 4-(4′-n-alkyloxyphenyl)phenyl 4-{2(S)-[2(S)-methylbutyloxy]propoxy}benzoate ( 4a-4f ) and 4 -(n-alkyloxy)phenyl 4-{4′-[2(S)-(2(S)-methylbutyloxy)propoxy]phenyl}benzoate ( 5a-5f ) were synthesized and their physical properties studied. A phase-transition sequence of C-Sc*-N*-I was observed in most cases. Some homologues of them, 4a-4d , possess monotropic Sc * phase. Not only the Sc* phase-transition temperature of 5a-5f is lower than that of the corresponding 4a-4f , but their Sc * phase-transition temperature range is also wider than the corresponding 4a-4f . The Sc * phase temperature range can be up to 48 °C. The spontaneous polarization of 8-28 nC/cm² and the electric rise time of 240-420 μs were measured in FLCs 4a-5f .     

C45- and C50-Carotinoide. 1. Mitteilung. Synthese von (R)- and (S)-Lavandulol

C₄₅- and C₅₀-Carotenoids, 1st Communication. Synthesis of (R)- and (S)-Lavandulol Starting with methyl (3 R)-3-hydroxybutanoate ((R)-7) and ethyl (3 S)-3- hydroxybutanoate ((S)- 11 ), respectively, (R)- and (S)-lavandulol ((R)- 1 and (S)- 1 ) were synthesized with high optical purity. The synthesized key intermediates (R)- 6 and (S)- 6 are suitable compounds for the synthesis of optically active acyclic C₄₅- and C₅₀-carotenoids.     

Asymmetric synthesis of (S,R)- and (R,R)-methiin stereoisomers

Abstract

An asymmetric synthesis of (+)- and (–)-methiine (S-methyl-(R)-cysteine sulfoxide) diastereomers has been developed. These natural sulfur compounds were isolated from a variety of Brassica vegetables. As the starting compound, (R)-cysteine was used, which was methylated to form (R)-S-methylcysteine. Then the oxidation of S-methylcysteine with tert-butyl hydroperoxide catalyzed by the chiral tetra(isopropylate)titanium/(S)- or (R)-Binol complex led to the formation of (1?R,2S)-(+)- or (1?R,2R)-(–)-methiin stereomers.     

Racemization of (S)-(+)-10,11-dimethoxyaporphine and (S)-(+)-aporphine: efficient preparations of (R)-(−)-apomorphine and (R)-(−)-aporphine via a recycle process of resolution

Efficient preparations of (R)-(−)-apomorphine (R)-1 and (R)-(−)-aporphine (R)-2 based on a recycle process of resolution are described. In this recycle process of resolution, (RS)-(±)-10,11-dimethoxyaporphine 3 as the precursor of 1, and (RS)-(±)-aporphine 2 were successfully resolved into both enantiomers with (+)-dibenzoyltartaric acid (DBTA). The desired (R)-3 and (R)-2 were obtained and then, respectively, transformed to compound (R)-1, the hydrochloride salt of (R)-1, diacetate compound 4 and the hydrochloride salt of (R)-2; while the undesired (S)-3 and (S)-2 were racemized to obtain a racemate, which was suitable for further resolution. A method for the racemization of the undesired (S)-3 and (S)-2 was extensively studied, in order to obtain high-yielding racemization conditions. A plausible mechanism for the racemization of (S)-3 and (S)-2 was also proposed.     

A Versatile Approach to Protected (S)-Aspartimide, (4S)-Amino-2-Pyrrolidinone and (3S)-Aminopyrrolidine From (S)-Aspartic Acid

Starting from (S)-aspartic acid, a versatile approach to (S)-l-benzyl-3-p-toluenesulfonylamino-2,5-pyrrolidinedione, (S)-l-benzyl-4-p-toluenesulfonylamino-2-pyrrolidinone and (S)-l-benzyl-3-p-toluenesulfonylaminopyrrolidine is described.     

Synthesis and Structure of 2,3-Bis(5-tert-butyl-2-methoxyphenyl)buta-1,3-diene by Bromine Elimination of (Z)-1,4-Dibromo-2,3-bis(5-tert-butyl-2-methoxyphenyl)-2-butene

2,3-Bis(5-tert-butyl-2-methoxyphenyl)buta-1,3-diene was prepared by bromination of (Z)- and (E)-2,3-bis(5-tert-butyl-2-methoxyphenyl)-2-butene followed by treatment with zinc powder in a mixture of CH₂Cl₂ and acetic acid, which was converted to the corresponding o-terphenyl skeleton by the condensation with dimethyl acetylenedicarboxylate followed by oxidation with 2,3-dichloro-5,6-dicyanobenzoquinone.     

An Efficient Synthesis of Optically Pure (R)- and (S)-2-(aminomethyl)alanine ((R)- and (S)-ama) and (R)- and (S)-2-(aminomethyl)leucine ((R)- and (S)-aml)

An efficient synthesis of enantiomerically pure (R)- and (S)-2-(aminomethyl)alanine ((R)- and (S)-Ama) 1a and (R)- and (S)-2-(aminomethyl)leucine ((R)- and (S)-Aml) 1b is described (Schemes 1 and 2). Resolution of the racemic amino acids was achieved using L -phenylalanine cyclohexylamide ( 2 ) as chiral auxiliary. The free amino acids 1a, b were converted to the N^α-Boc,N^γ-Z-protected derivatives 11a, b (Scheme 3) ready for incorporation into peptides. Based on the three crystal structures of the diastereoisomeric peptides 8a, 8b , and 9b , the absolute configurations in both series were determined. β-Turn type-I geometries were observed for structures 8b and 9b , whereas 8a crystallized in an extended backbone conformation.