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Tungsten(0)- and rhenium(I)-catalyzed reactions of acetylenic dienol silyl ethers based on the concept of geminal carbo-functionalization of alkynes are reported. Treatment of 3-siloxy-1,3-diene-7-ynes with catalytic amounts of [W(CO)6] or [ReCl(CO)5] under photoirradiation conditions gives synthetically useful bicyclo[3.3.0]octane derivatives in good yields. Extremely high catalytic activity is noted for the rhenium(I) complex. The reaction has been extended to substrates containing a nitrogen atom in their tethers. In this case, two kinds of synthetically useful heterocyclic compounds-the 2-azabicyclo[3.3.0]octane derivatives 9 and the monocyclic dihydropyrroles 10, with allenyl substituents-are obtained, and selective preparation of either product can be achieved through the use of an appropriate combination of the nitrogen substituent and the type of the rhenium(I) catalyst. The 2-azabicyclo[3.3.0]octane derivatives 9 are obtained selectively by carrying out treatment of N-Ns derivatives in the presence of [ReCl(CO) 4(PPh3)], whereas the dihydropyrrole derivatives 10 are obtained by treatment of N-Mbs derivatives with [ReCl(CO)5]/ AgSbF6. Finally, we have applied this geminal carbo-functionalization to one-carbon-elongated substrates containing N-Ts moieties in their tethers. Selective 5-exo cyclization is achieved in the presence of gold(I) or rhenium(I) catalysts, whereas 6-endo cyclization is observed on use of [W(CO) 6]. Geminal carbo-functionalization of 3-siloxy-1,3-dien-7-ynes leading to bicyclo[3.3.0]octane derivatives is achieved through electrophilic activation of alkynes by tungsten(0) and rhenium(I) catalysts (see graphic). Extremely high activity is noted for rhenium(I) catalysts. Furthermore, selective preparation of two different classes of heterocyclic compounds from 5-aza-3-siloxy-1,3-dien-7-ynes is also achieved by appropriate choice of the rhenium(I) catalyst and the protecting group on the nitrogen. 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

The Shocking Revelation of C17H14O

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The nonfluorinated parent dibenzalacetone 1 as well as the corresponding penta- (2) and decafluorinated (3) derivative compounds were prepared, crystallized, and subjected to co-crystallization experiments. Only 3 yielded a 1:1 co-crystal with 1, while 2 did not form co-crystals with either 1 or 3. Powder X-ray diffraction patterns were determined to verify the co-crystallization experiments. The influence of the fluorine on the molecular geometry and crystal packing were studied and comparatively discussed. Conclusions with reference to the priority of Ar…ArF contact modes in the crystalline packing being in competition with other fluorine and non-fluorine involved supramolecular interactions were drawn.

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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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Dibenzylidene and heterobenzylideneacetone derivatives, related 4-piperidones, related 4-thiopyranones and the corresponding sulfinyl- and sulfonyl-analogues for their use for prophylaxis or treatment of trypanosomiasis and leishmaniasis.

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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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The tris(cyanoethyl)phosphine (tcep) complexes trans-[PtCl2(tcep)2], cis-[PtMe2(tcep)2], and trans-[PtMeCl(tcep)2] are prepared by treatment of the corresponding [PtXY(cod)] (cod = 1,5-cyclooctadiene) with tcep. Reduction of trans-[PtCl2(tcep)2] with NaBH4 gives trans-[PtHCl(tcep)2] which, in the presence of tcep and NEt3, gives the coordinatively unsaturated platinum(0) complex [Pt(tcep)3]. This coordinatively unsaturated species is also formed when [Pt(norbornene)3] reacts with tcep. [Pt(tcep)3] is very unreactive compared to its PEt3 analogue: it is air-stable and does not react with further tcep to form an 18-electron species. It is protonated by HBF4 · OEt2 to form [PtH(tcep)3]BF4. The complex trans-[PdCl2(tcep)2] is made from [PdCl2(NCPh)2] and tcep and the derivatives trans-[PdX2(tcep)2] (X = Br or I) are made by metathesis of the dichloro complex. Reduction of trans-[PdCl2(tcep)2] with LiOMe in the presence of tcep gave the palladium(0) complex [Pd(tcep)3] which, like its platinum(0) analogue, undergoes exchange with free tcep on the NMR timescale. The palladium complex reacts with dibenzylideneacetone (dba) to form [Pd(eta2-dba)(tcep)2]; the same product is formed in the reaction of [Pd(eta2-dba)2] and tcep. Reaction of [Pd2Cl2(eta3-C3H3) 2] and tcep gives [PdCl(tcep)(eta3-C3H3)] or [Pd(tcep)2(eta3-C3H3)]Cl depending on stoichiometry. The rhodium(I) and iridium(I) complexes trans-[MCl(CO)(tcep)2], [MCl(tcep)(cod)] and [MCl(tcep)3] are all readily made from tcep and an appropriate precursor. All new compounds have been fully characterised by a combination of elemental analysis, IR, 31P, 13C, 1H and 195Pt NMR spectroscopy. The crystal structure of [IrCl(tcep)3] as a MeCN solvate shows a distorted square planar coordination geometry (trans angles at Ir(I) ca. 164, cis P-Ir-P av. 96, cis P-Ir-Cl av. 85). Analysis of the conformations of tcep ligands in this and other published tcep complexes shows there is a preference for conformations in which aaa, aag or g+g- (a = anti, g = gauche) arrangements of the three M-P-C-C chains are avoided.

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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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Syntheses of (2S,12’R)-2-(12′-aminotridecyl)-pyrrolidine (1) and (28,12’R)-1-(2′-hydroxyethyl)-2-(12′-aminotridecyl)-pyrrolidine (2), two defensive alkaloids recently isolated from the Mexican bean beetle, Epilachna varivestis, are described. By a comparison of 1H NMR data of MTPA derivatives of natural alkaloid 2 with those of the synthetic standard, we confirm the (2S,12’R) configuration previously suggested for this alkaloid. Further support of these assignments was provided by the synthesis and 1H NMR investigation of(2S,12’S)-1, (2S,12’S)-2, and their MTPA derivatives.

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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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Herein we describe a concise assembly of the central 1,6-dioxaspiro[4.4] nonane core of cephalosporolides E/F by employing a Pd-mediated alkynediol cycloisomerization and their total synthesis. On the basis of spectroscopic data and optical rotation values, the absolute configurations of cephalosporolides E/F were proposed.

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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

Interesting scientific research on (2S,3S)-Butane-2,3-diol

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2-Pyrones are frequently produced by microorganisms and often exhibit interesting bioactivities. Therefore, a short and easy synthetic access to these natural products is desirable. Synthetic routes to nectriapyrone, gibepyrone A, racemic gulypyrone A, (+)-germicidin C, (ent)-desoxygermicidin C and (ent)-prolipyrone A via a modular approach are presented, allowing the assignment of the absolute configurations of the latter three chiral compounds. The method failed for the synthesis of (ent)-phomapyrone B that was thus synthesized via a different route, resulting in an assignment of the absolute configuration of natural phomapyrone B.

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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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The encapsulation of homogeneous chiral catalysts, e.g. Co(Salen) and Ru-TsDPEN, in the mesoporous cage of SBA-16 is demonstrated; the encapsulated catalysts show performance as good as that of the homogeneous catalysts, and can be recycled for more than 10 times without significant loss of catalytic performance. The Royal Society of Chemistry.

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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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The highly enantioselective hydrolytic kinetic resolution (HKR) of racemic terminal epoxides by bimetallic chiral (salen)Co and (salen)Co(III)-OAc mixture provides a simple and effective method for the synthesis of enantiomerically enriched terminal epoxides (ee > 99%) and diols. At the equimolar amounts of bimetallic chiral (salen)Co and (salen)Co(II)-OAc, the catalytic activity increases more than two times in comparison with (salen)Co(III)-OAc used alone. The mixed catalytic system can be recycled and reused. No significant loss of catalytic activity was observed after three runs.

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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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Related Products of 538-58-9, New research progress on 538-58-9 in 2021. Redox catalysis has been broadly utilized in electrochemical synthesis due to its kinetic advantages over direct electrolysis. 538-58-9, Name is 1,5-Diphenylpenta-1,4-dien-3-one, molecular formula is C17H14O. In a article,once mentioned of 538-58-9

Photoexcitation of dibenzalacetones (1a-d) in homogeneous media and solid state yields a mixture of products with poor conversions. Irradiation of the reactants complexed to gamma-cyclodextrin predominantly affords a single dimer (syn adduct 6) despite the possibility for several monomeric and dimeric products. High selectivity in the cavitand-mediated reaction along with the structural characterization of the inclusion complex provides insight into the supramolecular interactions that drive the self-assembly of the host-guest system.

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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