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General and stereoselective aminoxylation of biradical titanium(iv) enolates with TEMPO: A detailed study on the effect of the chiral auxiliary

A comprehensive analysis of the influence of the chiral auxiliary on the alpha-aminoxylation of titanium(iv) enolates with TEMPO indicated that (S) 4-tert-butyl-1-oxazolidine-2-thione is the most appropriate scaffold to provide a single diastereomer in high yields for a variety of substrates, which converts such a radical reaction into a highly chemo- and stereoselective oxidation.

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Practical synthesis of chiral cis-cyclohex-4-ene-1,2-dicarboxylic acid derivatives by utilizing (4S)-isopropyl-1,3-thiazolidine-2-thione

Both enantiomers of chiral cis-cyclohex-4-ene-1,2-dicarboxylic acid derivatives were synthesized by optical resolution of the corresponding enantiomeric mixtures by utilizing (4S)-isopropyl-1,3-thiazolidine-2-thione followed by mild aminolysis, methanolysis, and hydrolysis.

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Synthesis of dysideaproline e using organocatalysis

(S)-4,4-Dichloro-3-methylbutanoic acid was prepared in 51% overall yield from commercially available starting materials using an organocatalytic transfer hydrogenation to 4,4-dichloro-3-methylbut-2-enal in the key step. The (S)-dichloro acid was used as an intermediate in the first total synthesis of dysideaproline E and a diastereomer confirming the structure of the natural product.

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New class of pyridine catalyst having a conformation switch system: Asymmetric acylation of various sec-alcohols

We have developed a new class of pyridine catalyst for asymmetric acylation of sec-alcohols having a conformation switch system in which interconversion between self-complexation and uncomplexation is induced by acylation and deacylation steps, respectively. Kinetic resolution of various sec-alcohols is performed by the asymmetric acylation with isobutyric anhydride using 0.05 to 0.5 mol % catalyst 1a with s values of up to 30. In addition, dl-diols are also resolved in a similar manner in good selectivity. Moreover, asymmetric desymmetrization of meso-1,X-diols (X = 2-6) are achieved in the presence of 0.5-5 mol % catalyst 1a. A working model for the reaction mechanism is proposed on the basis of the 1H NMR measurements, X-ray structural analyses, and AM1 and DFT calculations, where the conformation switch system governed by an intramolecular cation-pi interaction between a pyridinium ring and a thiocarbonyl group would play a key role to attain both good selectivity and high catalytic activity.

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Phosphorus-containing amino acids with a P-C bond in the side chain or a P-O, P-S or P-N bond: From synthesis to applications

Since the discovery of (l)-phosphinothricin in the year 1970, the development of alpha-amino acids bearing a phosphorus group has been of renewed interest due to their diverse applications, including their use in [18F]-fluorolabeling, as fluorescent probes, as protecting groups and in the reversible immobilization of amino acids or peptide derivatives on carbon nanomaterials. Considerable progress has also been achieved in the field of antiviral agents, through the development of phosphoramidate prodrugs, which increase significantly the intracellular delivery of nucleoside monophosphate and monophosphonate analogues. This review aims to summarize the strategies reported in the literature for the synthesis of P(iii), P(iv) and P(v) phosphorus-containing amino acids with P-C, P-O, P-S or P-N bonds in the side chains and their related applications, including their use in natural products, ligands for asymmetric catalysis, peptidomimetics, therapeutic agents, chemical reagents, markers and nanomaterials. The discussion is organized according to the position of the phosphorus atom linkage to the amino acid side chain, either in an alpha-, beta-, gamma- or delta-position or to a hydroxyl, thiol or amino group.

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Expeditious Asymmetric Synthesis of Optically Pure delta-Lactones Bearing Consecutive Three Asymmetric Centers

The (4S)-isopropyl-1,3-thiazolidine-2-thione diamides of 3-substituted glutaric acids were submitted to enolization with Sn(CF3SO3)2 and N-ethylpiperidine.The resultant tin(II) enolate was treated with several aldehydes to give the aldols, which readily undergo basic lactonization affording the corresponding chiral delta-lactones bearing consecutive three asymmetric centers.

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New C4-chiral 1,3-Thiazolidine-2-thiones: Excellent Chiral Auxiliaries for Highly Diastereocontrolled Aldol-Type Reactions of Acetic Acid and alpha,beta-Unsaturated Aldehydes

Diastereocontrolled aldol-type reactions between tin(II) enolates of 3-acetyl-4(S)-ETT (6a) and 3-acetyl-4(S)-IPTT (6b) and alpha,beta-unsaturated aldehydes 7a-c were successfully carried out to give, with highly diastereoselectivity, compounds 9a-e (major products) and 10a-e (minor products).The reaction conditions were also investigated in detail.

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Methods for the synthesis of carbon-13 labelled acids and esters

Syntheses of isotopically labelled putative biosynthetic intermediates to the natural products monocerin 1, hectochlorin 2 and strobilurin A 3 are described. For the preparation of [9,10-13C2] dihydroisocoumarin 10, a stereoselective aldol condensation of 13C2-acetylated chiral auxiliary 5 was used to assemble the labelled C9-C14 fragment. The preferred approaches to the syntheses of [1,2-13C2]5,5-dichlorohexanoic acid 15 and the N-acetylcysteamine derivative of [1,2-13C2]cinnamic acid 19 involved a Horner-Wadsworth-Emmons chain extension and Knoevenagel reaction, respectively. Copyright

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Total synthesis of the lipid mediator PD1n-3 DPA: Configurational assignments and anti-inflammatory and pro-resolving actions

The polyunsaturated lipid mediator PD1n-3 DPA (5) was recently isolated from self-resolving inflammatory exudates of 5 and human macrophages. Herein, the first total synthesis of PD1n-3 DPA (5) is reported in 10 steps and 9% overall yield. These efforts, together with NMR data of its methyl ester 6, confirmed the structure of 5 to be (7Z,10R,11E,13E,15Z,17S,19Z)-10,17- dihydroxydocosa-7,11,13,15,19-pentaenoic acid. The proposed biosynthetic pathway, with the involvement of an epoxide intermediate, was supported by results from trapping experiments. In addition, LC-MS/MS data of the free acid 5, obtained from hydrolysis of the synthetic methyl ester 6, matched data for the endogenously produced biological material. The natural product PD1 n-3 DPA (5) demonstrated potent anti-inflammatory properties together with pro-resolving actions stimulating human macrophage phagocytosis and efferocytosis. These results contribute new knowledge on the n-3 DPA structure-function of the growing numbers of specialized pro-resolving lipid mediators and pathways.

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DIASTEREOSELECTIVE ALKYLATION OF CHIRAL TIN(II) ENOLATES ONTO CYCLIC ACYL IMINIUM IONS. ASYMMETRIC TOTAL SYNTHESIS OF (-)-SUPINIDINE

The scope and mechanism of the asymmetric alkylation of chiral tin(II) enolate 10 with cyclic acyl iminium ion 5 were investigated.An application of the reaction to the asymmetric synthesis of (-)-supinidine was also achieved.

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