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The strong Br°nsted basic character of N-heterocyclic carbenes (NHCs) has been used to promote the cascade double Michael addition between fluorenes and dienones. Under catalyst loadings of 1?5 mol% of NHC, fluorene reacts with divinyl ketones (DVKs) to afford anti-spirofluorene compounds in high yields. However, when benzenedi(enones) were employed as Michael acceptors in the presence of 10 mol% of NHC, fluorene undergoes a different inter- and intramolecular cascade double Michael addition, providing multi-substituted indanes in high yields with excellent diastereoselectivity. (Figure presented.).

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A practical synthesis of (+)-aklavinone, the aglycone of antitumor antibiotic aclacinomycin A, is achieved by using the asymmetric aldol reaction of 6a to 10a as the key step.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Tin(IV) chloride and titanium(IV) chloride mediated cyclizations of the ortho-allyl-substituted homochiral hydroxyanthraquinone acetals (7)-(10), prepared by optimized reductive Claisen rearrangements, have afforded monochloro and dichloro tetracyclic products, the stereochemistry of which has been assigned by using n.m.r. techniques.An SN2-like process in which the dioxolan ring is maintained as an ion pair intermediate is favoured when either tin(IV) chloride or titanium(IV) chloride is used at -78 deg.Thereafter the direction of addition of chloride at C9 is largely governed by the orientation of this ion pair.An alternative path which probably involves a free oxocarbenium ion predominates at higher temperatures.An adjacent methoxy group on the anthraquinone lowers the stereoselectivity at both C7 and C9, possibly by bidentate coordination of the Lewis acid involving the quinone carbonyl, the methoxy oxygen and the acetal oxygens.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Four new chiral polymers of BINOLSalen-cobalt(III) salt complexes have been designed, synthesized and applied to the direct fabrication of chiral propylene carbonate from racemic propylene oxide. The (R/S)-polymer catalyst 2 and (S/R)-polymer catalyst 4 exhibit better enantioselectivity than the (R/R)-polymer catalyst 1 and the (S/S)-polymer catalyst 3 and have been recovered and reused more than ten times without loss of activity and enantioselectivity.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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This invention relates to pyrrolopyrimidine comprising compounds that may be useful as inhibitors of Mitogen-activated Protein Kinase Kinase Kinase Kinase-4 (MAP4K4). The invention also relates to the use of these pyrrolopyrimidine comprising compounds, for example in a method of treatment. There are also provided processes for producing compounds of the present invention and method of their use. In particular, the present invention relates to compounds of formula (I).

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

Properties and Exciting Facts About C4H10O2

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Two methylated bis(ethylenedithio)tetrathiafulvalene (ET) derivatives, Me2ET and Me4ET were stereoselectively synthesized to examine the effect of methylation on conformations of dihydrodithiin rings and molecular arrangements in the crystalline state.Since the donating ability of Me2ET and Me4ET are similar to that of ET, the methylated ET derivatives are considered to be appropriate to investigate the “lattice pressure” effect on ET radical salts by changing the volume of donor molecules.The upper limit of an activation energy for the ring inversion of the dimethylated dihydrodithiin in solution was estimated to be 32 kJ mol-1 by 13C NMR spectroscopy.The X-ray structure analyses revealed that orientations of methyl groups are fixed to axial in Me2ET and to equatorial in Me4ET, accompanied by the change of molecular stacking.The “volume of a methyl group” was evaluated by comparing the molecular volumes of Me2ET and Me4ET with that of ET, and the effective volume for the axial methyl group turns out to be 15percent larger than that of the equatorial.The solid state 13C NMR (CP/MAS) spectra of ET and its derivatives showed that the chemical shifts of resonance lines reflect the conformations of dihydrodithiin rings in crystals.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A novel RhCl(PPh3)3/BF3·OEt2 co-promoted direct C-C cross-coupling of primary and secondary alcohols at beta-position with aldehyde was developed. This reaction could provide an efficient synthesis of a series of alpha,beta-unsaturated aldehydes and diarylidene ketones, just from simple and easily available alcohols and aldehydes.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A gene encoding a stereo-specific secondary alcohol dehydrogenase (CpSADH) that catalyzed the oxidation of (S)-1,3-BDO to 4-hydroxy-2-butanone was cloned from Candida parapsilosis. This CpSADH-gene consisted of 1,009 nucleotides coding for a protein with M, 35,964. A recombinant Escherichia coli JM109 strain harboring the expression plasmid, pKK-CPA1, produced (R)-1,3-BDO (93.5% ee, 94.7% yield) from the racemate without any additive to regenerate NAD+ from NADH.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Atropos phosphoramidites with the D2-symmetric biphenyl backbone were diastereoselectively prepared with ease from achiral tetrahydroxy biphenyls. This type of ligands is proved to be highly efficient in the Cu-catalyzed conjugate additions of diethylzinc to alpha,beta-unsaturated ketones and nitroalkenes. The unique D2-symmetric backbone endows the ligands with an excellent chiral environment.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Spirocyclic azlactones are shown to be useful precursors of cyclic quaternary amino acids, such as the constrained cyclohexane analogues of phenylalanine. These compounds are of interest as building blocks for the synthesis of artificial peptide analogues with controlled folds in the peptide backbone. They were prepared in the present study by a step- and atom-economic catalytic asymmetric tandem approach, requiring two steps starting from N-benzoyl glycine and divinylketones. The key of this protocol is the enantioselective formation of the azlactone spirocycles, which involves a PdII-catalyzed double 1,4-addition of an in situ generated azlactone intermediate to the dienone (a formal [5+1] cycloaddition). As the catalyst, a planar chiral ferrocene bispalladacycle was used. Mechanistic studies suggest a monometallic reaction pathway. Although the diastereoselectivity was found to be moderate, the enantioselectivity is usually high for the formation of the azlactone spirocycles, which contain up to three contiguous stereocenters. Spectroscopic studies have shown that the spirocycles often prefer a twist over a chair conformation of the cyclohexanone moiety. A formal [5+1] cycloaddition of divinylketones and an in situ-generated glycine-derived azlactone was catalyzed by a chiral bis-palladacycle and provided highly enantioenriched, spirocyclic, masked amino acid products. The latter were used to synthesize biologically interesting constrained cyclohexane analogues of phenylalanine in just two steps (see scheme). Copyright

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate