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PROCESS FOR THE HYDROGENATION OF ESTERS OF ALPHA-SUBSTITUTED CARBOXYLIC ACIDS

There is provided a process for the hydrogenation of esters of alpha-substituted carboxylic acids which comprises reacting an ester of an alpha-substituted carboxylic acid with hydrogen in the presence of a catalyst under substantially homogeneous supercritical conditions. Preferably, the ester of an alpha-substituted carboxylic acids is an ester of formula (1): wherein: R1 and R2are each independently an optionally substituted hydrocarbyl group or an optionally substituted heterocyclic group; and Y is a heteroatom or an optionally substituted heteroatom group. More preferably, the ester of an alpha-substituted is carboxylic acids is an ester of formula (2): wherein: R3 is an optionally substituted hydrocarbyl group or an optionally substituted heterocyclic group; R4and R5 are each independently hydrogen, an optionally substituted hydrocarbyl group or an optionally substituted heterocyclic group; Y is a heteroatom or an optionally substituted heteroatom group; Q is a functional group; and n 1. Most preferably, the ester of an alpha-substituted carboxylic acids is an ester of formula (3): wherein: R3 and R6 are each independently an optionally substituted hydrocarbyl group or an optionally substituted heterocyclic group; R4 and R5 are each independently hydrogen, an optionally substituted hydrocarbyl group or an optionally substituted heterocyclic group; Y is a heteroatom or an optionally substituted heteroatom group; and n 1.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Synthesis and antiviral activity of methyl derivatives of 9-[2- (phosphonomethoxy)ethyl]guanine

A number of methyl derivatives of 9-[2-(phosphonomethoxy)ethyl]guanine (PMEG, 1) have been synthesized and tested in vitro for anti-herpes and anti- human immunodeficiency virus (HIV) activity. Among these analogues, (R)-2′- methyl-PMEG [(R)-3] and 2′,2′-dimethyl-PMEG (7) demonstrated potent anti-HIV activity in the XTT-assay with EC50 values of 1.0 and 2.6 muM, respectively. The corresponding (S)-2′-methyl-PMEG [(S)-3] was found to be less potent against HIV. In addition, the (R) and (S) enantiomers of 9-[3- hydroxy-2-(phosphonomethoxy)propyl]guanine (HPMPG, 8) were prepared for comparison of biological activity, and shown to be active and equipotent against herpesviruses, but inactive against HIV.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

More research is needed about (S)-Propane-1,2-diol

The prevalence of solvent effects in heterogeneous catalysis in condensed media has motivated developing quantitative kinetic, spectroscopic, and theoretical assessments of solvent structuresyou can also check out more blogs about4254-15-3 . name: (S)-Propane-1,2-diol

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Chiral phosphine-phosphite ligands with a substituted ethane backbone. influence of conformational effects in rhodium-catalyzed asymmetric olefin hydrogenation and hydroformylation reactions

A family of chiral (3,3?-di-tert-butyl-5,5?,6,6?- tetramethyl-2,2?-biphenol-derived) phosphine-phosphite ligands (P-OP) with a substituted ethane backbone has been synthesized and the performance of these ligands in the Rh-catalyzed enantioselective hydrogenation and hydroformylation of several representative olefins analyzed. Corresponding cationic rhodium complexes provide highly enantioselective catalysts for the hydrogenation of methyl (Z)-alpha-acetamidocinnamate (MAC) and dimethyl itaconate. The catalyst comparison indicates that, for the two substrates, product configuration is determined by the configuration of the phosphite. Regarding matching and mismatching effects in these hydrogenations, small effects were observed in the reduction of MAC, while for the itaconate the bigger difference between the matched and mismatched cases was of 21% ee. On the other hand, Rh catalysts based on P-OP ligands showed good levels of activity and regioselectivity in the hydroformylation of styrene and allyl cyanide, while moderate enantioselectivities were obtained. Participation of the two stereogenic elements has been observed in these reactions, and their mismatched combination leads to cancellation of enantioselectivity. To further investigate the influence of the ligand backbone in the course of these reactions, structures of rhodium model complexes Rh(Cl)(CO)(P-OP) were analyzed by DFT methods. The results obtained indicate the existence of two types of preferred conformations, whose relative stability depend on the backbone nature. Comparison of structures of the more stable conformers for each ligand indicates that the orientation of the biaryl phosphite group with respect to the coordination plane does not vary substantially along the series. Differently, the position of the phenyl phosphine substituents greatly depends on the backbone. On the basis of these observations it has been concluded that chiral induction in the hydrogenation is very predominantly due to the phosphite part of the ligand. Alternatively, conformation of the phosphine group has a great influence on enantioselectivity in the hydroformylation reactions, and even reversal of product configuration was observed between catalysts with an opposite axial equatorial arrangement of Ph phosphine substituents.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Synthesis and antiretroviral evaluation of new alkoxy and aryloxy phosphate derivatives of 3′-azido-3′-deoxythymidine

A series of new ether lipid-3′-azido-3′-deoxythymidine (AZT) conjugates (11a-g) were synthesized and evaluated for anti-HIV activity. The effect of chirality on the antiviral activity was examined through the synthesis of AZT conjugates bearing alkoxypropanols in the lipid portion of the molecule (11a-d). In addition, the long alkyl chain of alkoxyethyl ether lipid-AZT analogs was replaced with aromatic groups (11e-g), and the effect of this structural modification on activity is reported. The results of the biological tests indicate that analogs with a methyl group alpha to the phosphate moiety (11c,d) exhibit a marked degree of stereoselectivity with regard to their anti-HIV activity. Also, replacement of the long alkyl chain with aromatic groups in the oxyalkyl ether phospholipid-AZT conjugates leads to substantially more potent compounds (11e-g) with an anti-HIV activity comparable to that of AZT.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Copper-catalyzed cross-coupling of nonactivated secondary alkyl halides and tosylates with secondary alkyl grignard reagents

Practical catalytic cross-coupling of secondary alkyl electrophiles with secondary alkyl nucleophiles under Cu catalysis has been realized. The use of TMEDA and LiOMe is critical for the success of the reaction. This cross-coupling reaction occurs via an SN2 mechanism with inversion of configuration and therefore provides a general approach for the stereocontrolled formation of C-C bonds between two tertiary carbons from chiral secondary alcohols.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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The prevalence of solvent effects in heterogeneous catalysis in condensed media has motivated developing quantitative kinetic, spectroscopic, and theoretical assessments of solvent structuresyou can also check out more blogs about4254-15-3 . Application of 4254-15-3

Application of 4254-15-3, The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.4254-15-3, Name is (S)-Propane-1,2-diol, molecular formula is C3H8O2. In a Article£¬once mentioned of 4254-15-3

Resistance-modifying agents. 11. Pyrimido[5,4-d]pyrimidine modulators of antitumor drug activity. Synthesis and structure-activity relationships for nucleoside transport inhibition and binding to alpha1-acid glycoprotein

The cardiovascular and antithrombotic agent dipyridamole (DP) has potential therapeutic utility as a modulator of the activity of antimetabolite antitumor agents by virtue of its inhibition of nucleoside transport. However, the activity of DP can be compromised by binding to the acute phase serum protein, alpha1-acid glycoprotein (AGP). Analogues of DP were synthesized and evaluated as inhibitors of 3H-thymidine uptake into L1210 leukamia cells in the presence and absence of 5 mg/mL AGP. Compounds with potency similar to that of DP were identified where the piperidino substituents at the 4,8-positions were replaced by 4-methoxybenzylamino, 3,4-dimethoxybenzylamino, or piperonylamino groups. Replacement of the diethanolamino groups at the 2,6-positions of DP by alkylamino or alkoxy substituents was tolerated, although at least one oxygen-bearing function (hydroxyl or alkoxy) was required in the side chain for activity comparable to that of DP. Whereas AGP completely ablated the activity of DP, the majority of the newer compounds synthesized retained significant activity in the presence of excess AGP, although replacement of the piperidino groups at the 4,8-positions by N-methylbenzylamino substituents did, in some cases, restore susceptibility to AGP. Selected compounds have been demonstrated to prevent rescue from antifolate cytotoxicity, mediated by nucleoside salvage.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Induction of a preferred twist in a biphenyl core by stereogenic centers: A novel approach to the absolute configuration of 1,2- and 1,3-diols

A quick, simple, and reliable method to assign the absolute configuration of 1,2- and 1,3-diols: all that is needed is to measure the CD sign of the A band (250 nm) of their biphenyldioxolanes 1 (n = 0,1). The chirality of the diol induces a preferred sense of twist in the biphenyl moiety (R,R-M and S,S-P), and a positive A band (a probe of M twist) reveals an R or R,R configuration of the diol.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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PROCESS FOR THE PREPARATION OF DAPAGLIFLOZIN

The present invention discloses a novel process for the preparation of Dapagliflozin (S)-propylene glycol hydrate of Formula II. (Formula II)

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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AlEt3-promoted eliminative ring-opening of beta-hydroxy epoxides: Highly stereoselective synthesis of terminal alpha-hydroxy olefins

AlEt3-promoted eliminative ring-opening of beta-epoxy alcohols leading to alpha-hydroxy olefins is reported. This eliminative ring-opening reaction is shown to be highly stereoselective, thus providing an alternative asymmetric synthesis for alpha-hydroxy olefins.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Regio- and stereoselective glucosylation of diols by sucrose phosphorylase using sucrose or glucose 1-phosphate as glucosyl donor

Previously it has been shown that glycerol can be regioselectively glucosylated by sucrose phosphorylase from Leuconostoc mesenteroides to form 2-O-alpha-d-glucopyranosyl-glycerol (Goedl et al., Angew. Chem. Int. Ed. 47 (2008) 10086-10089). A series of compounds related to glycerol were investigated by us to determine the scope of the alpha-glucosylation reaction of sucrose phosphorylase. Both sucrose and glucose 1-phosphate (G1P) were applied as glucosyl donor. Mono-alcohols were not accepted as substrates but several 1,2-diols were readily glucosylated, proving that the vicinal diol unit is crucial for activity. The smallest substrate that was accepted for glucosylation appeared to be ethylene glycol, which was converted to the monoglucoside for 69%. Using high acceptor and donor concentrations (up to 2.5 M), sucrose or G1P hydrolysis (with H2O being the ‘acceptor’) can be minimised. In the study cited above, a preference for glucosylation of glycerol on the 2-position has been observed. For 1,2-propanediol however, the regiochemistry appeared to be dependent on the configuration of the substrate. The (R)-enantiomer was preferentialy glucosylated on its 1-position (ratio 2.5:1), whereas the 2-glucoside is the major product for (S)-1,2-propanediol (1:4.1). d.e. ps of 71-83% were observed with a preference for the (S)-enantiomer of the glucosides of 1,2-propanediol and 1,2-butanediol and the (R)-enantiomer of the glucoside of 3-methoxy-1,2-propanediol. This is the first example of stereoselective glucosylation of a non-natural substrate by sucrose phosphorylase. 3-Amino-1,2-propanediol, 3-chloro-1,2-propanediol, 1-thioglycerol and glyceraldehyde were not accepted as substrates. Generally, the glucoside yield is higher when sucrose is used as a donor rather than G1P, due to the fact that the released phosphate is a stronger inhibitor of the enzyme (in case of G1P) than the released fructose (in case of sucrose). Essentially the same results are obtained with sucrose phosphorylase from Bifidobacterium adolescentis.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate