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Direct alpha-siladifluoromethylation of lithium enolates with ruppert-prakash reagent via Ci-F bond activation

The direct alpha-siladifluoromethylation of lithium enolates with the Ruppert-Prakash reagent (CF3TMS) is shown to construct the tertiary and quaternary carbon centers. The Ruppert-Prakash reagent, which is versatile for various trifluoromethylation as a trifluoromethyl anion (CF3 -) equivalent, can be employed as a siladifluoromethyl cation (TMSCF2+) equivalent by Ci-F bond activation due to the strong interaction between lithium and fluorine atoms. Reaching for Ruppert-Prakash: The direct alpha-siladifluoromethylation of lithium enolates with the Ruppert-Prakash reagent (CF3TMS) is shown to construct tertiary and quaternary carbon centers (see scheme). The Ruppert-Prakash reagent can be employed as a siladifluoromethyl cation (TMSCF2+) equivalent by Ci-F bond activation due to the strong interaction between lithium and fluorine atoms.

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Synthesis of the ABCDEFG ring system of maitotoxin

Maitotoxin (1) continues to fascinate scientists not only because of its size and potent neurotoxicity but also due to its molecular architecture. To provide further support for its structure and facilitate fragment-based biological studies, we developed an efficient chemical synthesis of the ABCDEFG segment 3 of maitotoxin. 13C NMR chemical shift comparisons of synthetic 3 with the corresponding values for the same carbons of maitotoxin revealed a close match, providing compelling evidence for the correctness of the originally assigned structure to this polycyclic system of the natural product. The synthetic strategy for the synthesis of 3 relied heavily on our previously developed furan-based technology involving sequential Noyori asymmetric reduction and Achmatowicz rearrangement for the construction of the required tetrahydropyran building blocks, and employed a B-alkyl Suzuki coupling and a Horner-Wadsworth-Emmons olefination to accomplish their assembly and elaboration to the final target molecule.

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Isolation, biological activity evaluation, structure elucidation, and total synthesis of eliamid: A novel complex i inhibitor

Eliamid is a secondary metabolite isolated from two bacterial strains. This molecule features a linear polyketide backbone terminated by a tetramic acid amide moiety. Among other biological activities, eliamid shows a high and specific cytostatic action on human lymphoma and cervix carcinoma cell lines. The 2,4-anti relative configuration of the C-2,C-4-dimethyl substituted amide fragment was assigned by means of Breit’s rule. The absolute configuration of all stereocenters was determined by a combination of degradation methods, structural similarity analysis and total synthesis. The stereogenic centers were introduced by vinylogous Mukaiyama aldol reaction and two consecutive Myers alkylations. The use of pentafluorophenyl ester as acylation agent allowed the efficient formation of tetramic acid amide. The longest linear sequence in the synthesis consist of 13 steps and proceeds with 12 % overall yield. Differential spectroscopy experiments with beef heart submitochondrial particles established that eliamid is a potent inhibitor of the NADH-ubiquinone oxidoreductase complex. Additionally, biosynthesis of eliamid was investigated by feeding experiments with 13C-labeled precursors. How valuable is Breit’s rule? Isolation, biological activity profiling, structure elucidation and total synthesis of polyketide natural product eliamid are reported. This molecule is characterized by a tetramic acid amide fragment, which is rather rare among secondary metabolites isolated from myxobacteria. Copyright

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Kinetic resolution of 2-oxazolidinones via catalytic, enantioselective N-acylation

Kinetic resolution of racemic 2-oxazolidinones via catalytic, enantioselective N-acylation has been achieved for the first time and with outstanding selectivities. Copyright

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Preparation and Characterization of [5-13C]-(2S,4R)-Leucine and [4-13C]-(2S,3S)-Valine – Establishing Synthetic Schemes to Prepare Any Site-Directed Isotopomer of L-Leucine, L-Isoleucine and L-Valine

In this paper a chemo-enzymatic method has been developed that gives access to any isotopomer of the essential amino acids isoleucine and valine. The method gives the correct introduction of the second chiral center in (2S,3S)-isoleucine and allows for discrimination between the two prochiral methyl groups in valine as shown by the preparation of (2S,3S)-[4- 13C] valine. For the preparation of (2S)-leucine in any isotopomeric form, the O’Donnell method to prepare optically active amino acids has been used. The protected glycine scaffold used in this method has been prepared by a strategy that allows access to any isotopomeric form. The preparation of [5-13C]-(2S,4R)-leucine shows that the O’Donnell method in combination with the Evans method to obtain chiral 2-methylpropyl iodide leads to a good discrimination between the two prochiral methyl groups. The O’Donnell strategy for the preparation of alpha-amino acids is preferred over other methods since the reaction conditions are mild, the chiral auxiliary can be easily recovered and the optically active product can be easily separated. For the preparation of isotopically enriched valine and isoleucine the O’Donnell method is not suitable, because the alkyl substituents involved have a secondary halide substituent which is sterically too hindered to give an effective reaction with the protected glycine. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

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A LCZ – 696 for the preparation of key intermediate (by machine translation)

The present invention provides a novel method for preparing anti-heart failure drug LCZ – 696 of the key intermediate (2 R, 4 S) – 5 – (biphenyl – 4 – yl) – 4 – [(tert-butoxy carbonyl) amino] – 2 – methyl valeric acid method, the reaction route is as follows: The present invention provides a preparation method of simple synthetic route, the operation is simple, low cost, easy to realize industrial production. (by machine translation)

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Novel approach to stereoselective synthesis of (E)/(Z)-(N-acyl-oxazolidinone)-eneglycinates

(E)-(N-Acyl-oxazolidinone)-eneglycinates were synthesized with high stereoselectivity and in good yield by condensation of aldehydes with glycinates. (Z)-Eneglycinates could be prepared in high purity and moderate yield by transformation of (E)-eneglycinates under mild conditions. The effect on the (E)/(Z)-configuration of eneglycinates of steric hindrance by I¡À-substituents on the aldehyde was also examined. The software MMFF94 was used to explain the transformation of the thermodynamic product into the kinetic product and a plausible mechanism is given.

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[…] intermediate and its preparation method and application (by machine translation)

The invention discloses […] intermediate and its preparation method and application. The […] intermediates have the following formula III and/or formula IV shown in chemical structure shown in chemical structure. Wherein R is phenyl, benzyl, isopropyl; the application of the invention intermediate synthesis […], the preparation process is simple, mild reaction conditions, environmental protection and the like. To realize the low-cost, large-scale, high efficiency for preparing high-purity […] has important significance and use value. (by machine translation)

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AHU – 377 preparation method of the midbody and intermediate and intermediate preparation method (by machine translation)

The invention relates to the field of chemical synthesis, in particular to a AHU – 377 preparation method of the midbody and intermediate and intermediate preparation method. Formula (I) indicated by the AHU – 377 intermediate preparation method, the method comprising the formula (II) compound of formula (III) compounds are shown by the substitution reaction after hydrolysis of the formula (I) through the indicated by the AHU – 377 of the intermediate, the hydrolysis reaction of the hydrogen peroxide and hydrated lithium is carried out in the presence: Another purpose of this invention is to provide a novel compound, having a structure of formula (II) as shown: In the new route of the present invention, the formula (II) compound of formula (III) shown in preparation to obtain new compounds of formula (IV) as shown in the, selectivity is very good, generated during the reaction process of a very low amount of diastereoisomers, these thimbleful diastereoisomer also only needs through simple post-treatment can be removed. (by machine translation)

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A Novel Allyl Transfer Coupled with a Grob Fragmentation

A novel acid-promoted rearrangement is disclosed. In the previously unknown transformation, an allyl group migrated to an in situ formed carbocation stabilized by an electron-rich aryl or heteroaryl group, resulting in a stereoselective intramolecular Grob fragmentation. The outcome of the rearrangement observed with an array of substrates can be satisfactorily rationalized using a working hypothesis with the aid of a six-membered transition state similar to those proposed for the anionic oxy-Cope or oxonia-Cope rearrangements, but involving only one instead of two double bonds.

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