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Desulfurization-oxygenation of chiral 1,3-thiazolidine-2-thiones and 1,3-oxazolidine-2-thiones using propylene oxide and microwave irradiation

An efficient method for the desulfurization-oxygenation of 1,3-thiazolidine-2-thiones and 1,3-oxazolidine-2-thiones using propylene oxide and employing microwave irradiation is described. This strategy of oxygenation of the thiocarbonyl group provides an attractive methodology to prepare chiral 1,3-thiazolidin-2-ones and 1,3-oxazolidin-2-ones from the corresponding precursors in good yields. Copyright

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Quinuclidine – Wikipedia,
Quinuclidine | C7H740N | ChemSpider

A new application about (S)-4-Isopropylthiazolidine-2-thione

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Synthesis of polycyclic benzofused nitrogen heterocycles via a tandem ynamide benzannulation/ring-closing metathesis strategy. Application in a formal total synthesis of (?)-FR900482

A two-stage “tandem strategy” for the synthesis of benzofused nitrogen heterocycles is described that is particularly useful for the construction of systems with a high level of substitution on the benzenoid ring. The first stage in the strategy involves a benzannulation based on the reaction of cyclobutenones with ynamides. This cascade process proceeds via a sequence of four pericyclic reactions and furnishes a multiply substituted aniline derivative which can bear a variety of functionalized substituents at the position ortho to the nitrogen. In the second stage of the tandem strategy, ringclosing metathesis generates the nitrogen heterocyclic ring. This two-step sequence provides efficient access to highly substituted dihydroquinolines, benzazepines, benzazocines, and related benzofused nitrogen heterocyclic systems. The application of this chemistry in a concise formal total synthesis of the anticancer agents (?)-FR900482 and (?)-FR66979 is described. 2011 American Chemical Society.

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Quinuclidine – Wikipedia,
Quinuclidine | C7H736N | ChemSpider

More research is needed about (S)-4-Isopropylthiazolidine-2-thione

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Total Enantioselective Synthesis of the Endophytic Fungal Polyketide Phomolide H and Its Structural Revision

A total synthesis of the proposed structure of the natural polyketide-macrolactone phomolide H 2 has been achieved following a bidirectional strategy from l-tartaric acid. The originally assigned structure of phomolide H displayed discordant NMR spectroscopic data in comparison with synthetic 2. The synthetic strategy was extended to prepare diastereomers and epimeric methyl-ethers of the natural product, structural analysis of which revealed a match of the natural product with diastereomer 27. The structural revision of phomolide H from 2 to the methanol solvate of compound 27 is presented.

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Quinuclidine – Wikipedia,
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Reference of 76186-04-4, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.76186-04-4, Name is (S)-4-Isopropylthiazolidine-2-thione, molecular formula is C6H11NS2. In a article£¬once mentioned of 76186-04-4

Asymmetric Acylation of sec-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center

This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and 1H and 13C NMR spectroscopies and AMI calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.

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Quinuclidine – Wikipedia,
Quinuclidine | C7H760N | ChemSpider

Properties and Exciting Facts About (S)-4-Isopropylthiazolidine-2-thione

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Diastereoselective synthesis of cyclosaligenyl-nucleosyl-phosphotriesters

A diastereoselective synthesis of cycloSal-phosphotriesters (cycloSal=cycloSaligenyl) based on chiral auxiliaries has been developed that allows the synthesis of single diastereomers of the cycloSal-pronucleotides. In previously described synthesis routes, the cycloSal-compounds were always obtained as 1:1 diastereomeric mixtures that could be separated in only rare cases. However, it was shown that the diastereomers have different antiviral activity, toxicity, and hydrolysis stabilities. Here, first a chiral thiazoline derivative was used to prepare nonsubstituted and 5-methyl-cycloSal- phosphotriesters in 48 and ?95%a de (de=diastereomeric excess). However, this approach failed to give the important group of 3-substituted cycloSal-nucleotides. Therefore, two other chiral groups were discovered that allowed the synthesis of (RP)- and (SP)-3-methyl-cycloSal- phosphotriesters as well. The antiviral activity was found to be five- to 20-fold different between the two individual diastereomers, which proved the importance of this approach. Chiral chemical Trojan horses: cycloSal-nucleotides (cycloSal=cycloSaligenyl) of thymidine and cycloSal-pronucleotides of 3?-azido-3?-deoxythymidine (AZT) and 3?-deoxy-2?, 3?-didehydrothymidine (d4T) were prepared by a diastereoselective route for the first time by using a chiral auxiliary approach with up to ?95%a de (see scheme). The procedure is suitable to synthesize cycloSal-phosphotriesters with different substitution patterns in the aromatic residue.

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Quinuclidine – Wikipedia,
Quinuclidine | C7H751N | ChemSpider

The important role of 76186-04-4

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Computer-Guided total synthesis of natural products. Recent examples and future perspectives

Quantum chemical calculations of nuclear magnetic resonance (NMR) shifts and coupling constants have been extensively employed in recent years mainly to facilitate structural elucidation of organic molecules. When the results of such calculations are used to determine the most likely structure of a natural product in advance, guiding the subsequent synthetic work, the term ?computer-guided synthesis? could be coined. This review article describes the most relevant examples from recent literature, highlighting the scope and limitations of this merged computational/experimental approach as well.

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Quinuclidine – Wikipedia,
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Discovery of 76186-04-4

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Enantioselective synthesis of structurally intricate and complementary polyoxygenated building blocks of spongistatin 1 (altohyrtin a)

Enantioselective approaches to the construction of four complex building blocks of the structurally intricate marine macrolide known as spongistatin 1 are presented. The first phase of the synthetic effort relies on a practical approach to a desymmetrized, enantiomerically pure spiroketal ring system incorporating rings A and B. Concurrently, the C17-C28 subunit, which houses one-fifth of the stereogenic centers of the target in the form of rings C and D, was assembled via a composite of stereocontrolled aldol condensations. Once arrival at the entire C1-C28 sector had been realized, routes were devised to provide two additional highly functionalized sectors consisting of C29-C44 and C38-C51. A series of subsequent transformations including cyclization of the E ring and hydroboration to afford the B-alkyl intermediate for the key Suzuki coupling to append the side chain took advantage of efficient stereocontrol. Ultimately, complete assembly and functionalization of the western EF sector of spongistatin was thwarted by an inoperative Suzuki coupling step intended to join the side chain to the C29-C44 sector, and later because of complications due to protecting groups, which precluded the complete elaboration of the late stage C29-C51 intermediate.

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Quinuclidine – Wikipedia,
Quinuclidine | C7H719N | ChemSpider

Extracurricular laboratory:new discovery of (S)-4-Isopropylthiazolidine-2-thione

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Diastereoselective additions of titanium enolates from N-glycolyl thiazolidinethiones to acetals

The stereochemical outcome of the Lewis acid-mediated glycolate addition of the titanium enolates from protected N-hydroxyacetyl-4-isopropyl-1,3- thiazolidine-2-thiones to dimethyl and dibenzyl acetals depends on the hydroxyl protecting group. Particularly, the pivaloyl protected glycolate derivative provides the reluctant anti adducts in high yields and diastereomeric ratios, which can be isolated and further converted in enantiomerically pure form to beta-methoxy or beta-benzyloxy alpha-pivaloyloxy carbonyl fragments in a straightforward manner.

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Quinuclidine – Wikipedia,
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Top Picks: new discover of (S)-4-Isopropylthiazolidine-2-thione

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Reference of 76186-04-4, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 76186-04-4, molcular formula is C6H11NS2, introducing its new discovery.

Desulfurilative self-coupling reaction of 1,3-thiazolidine-2-thiones and intramolecular non-bonded S?S interaction in the crystallographic structure of the products

An attempt at an asymmetric Pummerer-type reaction of trans-4-benzyloxythiane-1-oxide (1) with 3-trifluoroacetyl-4S-isopropyl-1,3-thiazolidine-2-thione (2) resulted in failure but an attractive desulfurilative self-coupling reaction of 4S-isopropyl-1,3-thiazolidine-2-thione (6) occurred to give 4S-isopropyl-3-(4S-isopropyl-1,3-thiazolin-2-yl)-1,3-thiazolidine-2-thione (5). The same desulfurilative self-coupling reaction of compound 6 or 11 efficiently proceeded by treatment of diphenyl sulfoxide (7a) or methyl phenyl sulfoxide (7b) with 2 or 3-trifluoroacetyl-1,3-thiazolidine-2-thione (8) to afford each corresponding product 5 or 9. Eventually, we found a practically useful method for the synthesis of 5 and 9 by exploiting TiCl4 and sodium salt 12 or 13 of 1,3-thiazolidine-2-thiones. Interestingly, intramolecular non-bonded S?S interactions were recognized in the crystallographic structures of 5 and 9.

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Quinuclidine – Wikipedia,
Quinuclidine | C7H748N | ChemSpider

Discovery of (S)-4-Isopropylthiazolidine-2-thione

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Synthesis of the anti-HIV agent (-)-hyperolactone C by using oxonium ylide formation-rearrangement

Starting from readily available (S)-styrene oxide an asymmetric synthesis is described of the naturally occurring anti-HIV spirolactone (-)-hyperolactone C, which possesses adjacent fully substituted stereocenters. The key step involves a stereocontrolled RhII-catalysed oxonium ylide formation-[2,3] sigmatropic rearrangement of an alpha-diazo-beta-ketoester bearing allylic ether functionality. From the resulting furanone, an acid-catalysed lactonisation and dehydrogenation gives the natural product.

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Quinuclidine – Wikipedia,
Quinuclidine | C7H731N | ChemSpider