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A new steroidal-platinum(II) hybrid compound was synthesized using a simple and efficient methodology. The synthesis was performed by a convergent approach with cross metathesis (CM) as a key step. An olefin derived from lithocholic acid and a vinyl substituted ethylenediamine derived from L-serine were used as chiral building blocks, which were combined in the CM step. The most important advantage of this method was the utilization of L-serine as a cheap, stereoisomerically pure substrate. A steroid with a diamino system in the side chain was subjected to reaction with potassium tetrachloroplatinate to obtain the target platinum(II) complex. Attempts to synthesize similar diamine systems using the asymmetric Strecker reaction were unsuccessful.

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Nosiheptide is a ribosomally synthesized and post-translationally modified thiopeptide natural product that possesses antibacterial, anticancer, and immunosuppressive properties. It contains a bicyclic structure composed of a large macrocycle and a unique side-ring system containing a 3,4-dimethylindolic acid bridge connected to the side chains of Glu6 and Cys8 of the core peptide via ester and thioester linkages, respectively. In addition to the structural peptide, encoded by the nosM gene, the biosynthesis of the side-ring structure requires the actions of NosI, -J, -K, -L, and -N. NosN is annotated as a class C radical S-adenosylmethionine (SAM) methylase, but its true function is to transfer a C1 unit from SAM to C4 of 3-methyl-2-indolic acid (MIA) with concomitant formation of a bond between the carboxylate of Glu6 of the core peptide and the nascent C1 unit. However, exactly when NosN performs its function during the biosynthesis of nosiheptide is unknown. Herein, we report the syntheses and use of three peptide mimics as potential substrates designed to address the timing of NosN’s function. Our results show that NosN clearly closes the side ring before NosO forms the pyridine ring and most likely before NosD/E catalyzes formation of the dehydrated amino acids, although the possibility of a more random process (i.e., NosN acting after NosD/E) cannot be ruled out. Using a substrate mimic containing a rigid structure, we also identify and characterize two reaction-based adducts containing SAM fused to C4 of MIA. The two SAM adducts are derived from a consensus radical-containing species proposed to be the key intermediate – or a derivative of the key intermediate – in our proposed catalytic mechanism of NosN.

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Oxazolidine – Wikipedia,
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The unusual sphingoid base 5-hydroxy-3-sphingenine was identified in the hydrolysate of brain sphingolipids more than 40 years ago. We present here the first synthesis of the 5R and 5S diastereoisomers of the N-acyl derivatives of 5-hydroxy-3-sphingenine, 2 and 3, respectively, which represent regioisomers of (2S,3R)-ceramide (1). The key steps include the synthesis of a,beta-unsaturated ketone intermediates 4 and 5 from N-Cbz- and N-Boc -L-serine and diastereoselective reduction of the enones. The configuration at the new carbinol center was deduced by proton NMR analysis of (R)- and (S)-Mosher [methoxy(trifluoromethyl)phenylacetate] ester derivatives. Ceramide analogues 2 and 3 showed a markedly higher antiproliferative activity than 1 on MCF-7 cells.

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Oxazolidine – Wikipedia,
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A new, short (6 steps) and efficient enantiodivergent route to both D-erythro and L threo-sphingosine I and II is disclosed. The high diastereoselection (100% de) reached in the creation of the C-3 stereocenter relies on the use of a sulfoxide as chiral controlling agent in the reduction of the common precursor beta-keto sulfoxide 3. The desired E-alkene of sphingosines has been constructed by the Schlosser modification of the Wittig reaction between the aldehyde 8 and the phosphonium salt 9. The reported methodology can easily be extended to the synthesis of a large number of optically pure syn and anti amino alcohols starting from commercially available amino acids.

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An improved procedure for the preparation of 1,1-dimethylethyl 2.2-dimethyl-4-(S)-formyloxazolidine-3-carboxylate (Garner aldehyde) is described which avoids the need for methyl iodide and benzene. Elaboration of this aldehyde into the novel chiral building blocks mentioned in the title is also described.

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Sulfoxide and sulfone intermediates 7 and 15, respectively, were employed to synthesize synthons 3 and 4, which are readily converted to the naturally occurring (2S,3R,4(E))-sphingosine 1 and (2S,3R)-sphinganine 2.

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The present invention relates generally to substituted isoquinolines and their use as tubulin polymerization inhibitors. In particular, the invention relates to substituted isoquinolines which possess useful therapeutic activity, use of these compounds in methods of therapy and the manufacture of medicaments as well as compositions containing these compounds

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(Chemical Equation Presented) Chiral 1-aryl-6-(hydroxymethyl)-2- ketopiperazines can be prepared via an operationally simple, 6-exo epoxide ring-opening cyclization to form the ketopiperazine C6-N1 bond in high yields and with excellent enantiomeric purity.

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(Equation presented) Enantiomerically pure 5-acetyl-3-amino-3,4-dihydro-2H- 1-benzopyran and methyl 3-amino-3,4-dihydro-2H-1-benzopyran-5-carboxylate were successfully synthesized starting from D- or L-serine. The formation of the benzopyran ring involved a radical cyclization step. The enantiomeric purities of the final aminochroman derivatives were determined by capillary electrophoresis using beta-cyclodextrins as a chiral selector.

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Oxazolidine – Wikipedia,
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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 95715-86-9, name is Methyl (R)-N-Boc-2,2-dimethyloxazolidine-4-carboxylate, introducing its new discovery. Quality Control of Methyl (R)-N-Boc-2,2-dimethyloxazolidine-4-carboxylate

Optically active acyclic N-allylamino compounds with defined configurated trisubstituted double bonds were generated via a three step sequence. The first crucial step was a two-carbon chain elongation of chiral alpha-aminoacid esters succeeding in a Claisen ester condensation with acetic acid ester enolates. The so formed beta-ketoesters were subjected to a one pot procedure of an enol trifluoromethanesulfonate generation and a consecutive palladium catalysed cross-coupling: A Stille or a Sonogashira type reaction allowed to generate selectively the trisubstituted E-olefins.

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Oxazolidine – Wikipedia,
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