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Precision ADMET polyolefins containing dithiane: Synthesis, thermal properties, and macromolecular transformation

1,3-Dithiane and its derivatives are widely used as powerful acyl anion equivalent to a range of useful transformations that are needed in the synthesis of natural products. In this work, a series of polyolefins containing pendant dithiane groups have been designed and synthesized via acyclic diene metathesis polymerization (ADMET) polymerization and subsequent hydrogenation. The structures of these polymers were characterized by 1H NMR, 13C NMR, and FT-IR, and successful incorporation of the dithiane groups was proved. With different contents of the dithiane moieties, these ADMET polymers exhibited distinct thermal properties different from each other as evidenced by differential scanning calorimetry and thermal gravimetric analysis. The dithiane units in the ADMET polymer with 20 methylene carbons between the adjacent dithiane groups were transformed into thiol groups via reaction with Bu3SnH. This work provided a convenient route to synthesize polyethylene with pendant thiol groups that are evenly distributed in the chain.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Novel organometallic compound having high metathesis activity and method for preparation thereof, metathesis reaction catalyst comprising the compound, method of polymerization using the catalyst, and polymer produced by the method of polymerization

The present invention provides an organometallic compound represented by the general formula (1) or (2), process for producing the same, metathesis reaction catalyst containing the same, polymerization process using the same catalyst and polymer produced by the same polymerization process: 1

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Rate enhancement by ethylene in the ru-catalyzed ring-closing metathesis of enynes: Evidence for an “ene-then-yne” pathway that diverts through a second catalytic cycle

(Chemical Equation Presented) Mixing it: A dual-substrate/dual isotopic labeling strategy has shown that the accelerating effect of ethylene in intermolecular ring-closing metathesis of enynes is best explained by an ene-then-yne mechanism rather than the commonly proposed yne-then-ene mechanism (see picture).

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Chiral oxime ethers in asymmetric synthesis. O-(1-Phenylbutyl)- benzyloxyacetaldoxime, a versatile reagent for the asymmetric synthesis of protected 1,2-aminoalcohols, alpha-amino acid derivatives, and 2-hydroxymethyl nitrogen heterocycles including iminosugars

Addition of a range of organolithium and Grignard reagents to (E)-O-(1-phenylbutyl)benzyloxyacetaldoxime 1 in the presence of boron trifluoride dietbyl etherate is highly diastereoselective. The resulting hydroxylamines 2 undergo N-O bond cleavage upon treatment with zinc-acetic acid or molybdenum hexacarbonyl to give, after N-protection, protected 1,2-aminoalcohols 3 in high enantiomeric purity. Debenzylation of 3a and 3d gave N-Boc (R)-alaninol and (S)-phenylalaninol respectively. The hydroxylamines 2 also serve as alpha-amino acid precursors, 2i being converted into N-formyl-(R)-alaninyl-(S)-(4-bromo)phenylalanine ester 7, the N-terminal dipeptide of a natural depsipeptide. The versatility of the 1,2-aminoalcohol derivatives was further illustrated by their conversion into 5-, 6- and 7-membered 2-hydroxymethyl nitrogen heterocycles 15-19 in high enantiomeric excess by a ring-closing metathesis reaction. Further reaction of the dihydropyrrole 15 gave the iminosugar 1,4-dideoxy-1,4-imino-D-ribitol. The Royal Society of Chemistry 2005.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Regio- and stereoselective ring-opening dimerization-cross-coupling metathesis of 7-oxanorbornene derivatives

A new metathesis-based route for the linking of two tetrahydrofuran moieties by an ethylene subunit has been developed. Treatment of an optically pure 2-substituted 7-oxanorborn-5-ene with Grubbs’ ruthenium catalyst in the presence of allyl acetate afforded the product of two successive ring-opening metatheses and cross-metathesis in a highly regioselective fashion.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Catalytic ring-closing metathesis of doubly armed, bridged bicyclic sulfones. Evaluation of chain length and possible intramolecular SO2 group ligation to the ruthenium carbenoid

Disubstituted bicyclic sulfones 3a-3d, which were prepared by the 2-fold alkylation of 1,6-dilithio-9-thiabicyclo[4.2.1]nonane dioxide, undergo ring- closing metathesis to give a select few of the possible dimers and trimers. Only in the case of 3d were monomeric end products formed. The pronounced diastereoselectivities observed, particularly with the two lowest homologues, are suggested to be kinetically favored because of the operation of internal ruthenium/sulfonyl oxygen coordination during generation of the first intermolecular double bond. This ligation appears to be an important component of the overall reaction in that it serves to maximize unfavorable nonbonded steric interactions when the sulfone bridges adopt a syn relationship. MM3 calculations indicate the anti sulfone dimers also to be thermodynamically favored when n = 3. The preference for the anti sulfone arrangement appears to erode with an increase in the length of the tethers. Not unexpectedly, a ring size dependency is likely at play. The development of a ring-closing metathesis strategy for the incorporation of sulfone groups into stereochemically defined polybicyclic molecules has been realized.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Alkene Metatheses in Transition Metal Coordination Spheres: Effect of Ring Size and Substitution on the Efficiencies of Macrocyclizations that Join Trans Positions of Square-Planar Platinum Complexes

Reactions of KPPh2 and Br(CH2)nCH=CH 2 give the phosphines PPh2(CH2) nCH=CH2 (n = a, 4; b, 6; c, 8; d, 9; 95-41%), which are combined with the platinum tetrahydrothiophene complex [Pt(mu-Cl)(C 6F5)(S(CH2CH2-)2)] 2 to give trans-(Cl)(C6F5)Pt(PPh 2(CH2)nCH=CH2)2 (3a-d, 71-54%). When treated with Grubbs’ catalyst, ring-closing alkene metatheses occur to give 13- to 23-membered macrocycles with trans-spanning diphosphine ligands (96-85%, including some dimeric or oligomeric byproducts). The mixtures of C=C isomers are hydrogenated (1 atm, 10% Pd/C) to give trans-(Cl)(C 6F5)Pt(PPh2(CH2) 2n+2PPh2) (6a-d), which are isolated in 72-50% yields. Comparable results are obtained with (1) the second-generation dihydroimidazolylidene Grubbs’ catalyst and (2) a series of compounds derived from the dimethylated phosphine Ph2P(CH2) 2C(CH3)2(CH2)3CH=CH 2, in turn prepared by sequential reactions of BrCH 2CH2C(CH3)2CH2CH 2Br with BrMgCH2CH=CH2/Li2CuCl 4 and KPPh2. The crystal structures of 6a-d are analyzed, but no special features that would promote intramolecular macrocyclizations are noted. A reaction of [Pt(mu-Cl)(C6F5)(S(CH 2CH2-)2)]2 and the diphosphine Ph2P(CH2)14PPh2 leads to a multitude of products and little 6b (<15%). Do you like my blog? If you like, you can also browse other articles about this kind. 172222-30-9Thanks for taking the time to read the blog about 172222-30-9

Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Regarding the mechanism of olefin metathesis with sol-gel-supported Ru-based complexes bearing a bidentate carbene ligand. Spectroscopic evidence for return of the propagating Ru carbene

Two isotopically and structurally labeled Ru-based carbenes (2-d 4 and 13) have been prepared and attached to the surface of monolithic sol-gel glass. The resulting glass-supported complexes (18-d n and 19) exhibit significant catalytic activity in promoting olefin metathesis reactions and provide products of high purity. Through analysis of the derivatized glass pellets used in a sequence of catalytic ring-closing metathesis reactions mediated by various supported Ru carbenes, it is demonstrated that free Ru carbene intermediates in solution can be scavenged by support-bound styrene ether ligands prior to the onset of competing transition metal decomposition. The observations detailed herein provide rigorous evidence that the initially proposed release/return mechanism is, at least partially, operative. The present investigations shed light on a critical aspect of the mechanism of an important class of Ru-based metathesis complexes (those bearing a bidentate styrene ether ligand).

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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In a glove box, NHC ligand precursor 23 (162 mg, .34 mmol), ruthenium precursor 5 (150 mg, .27 mmol) and KOt-Bu(Fe) (74 mg, .34 mmol) were combined in C6D6 and stirred at RT for 2.5 hours. The flask was sealed, removed from the glove box and the reaction was concentrated and purified by flash column chromatography (2.5percent – > 5percent Et2psi/Pent) to yield a brown oil. The brown oil was lyophilized from benzene to give 25 as a brown solid (66 mg, 25percent). 1H NMR (300 MHz3 CDCl3) delta 20.07 (d, J = 10.5 Hz, IH)3 8.03 (br, 2H), 7.60 (t, 1.8 Hz, IH), 6.86-6.81 (ra, 2H), 6.51 – 6.47 (m, IH), 1.81 – 1.07 (m).

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Reference£º
Patent; MATERIA, INC.; CALIFORNIA INSTITUTE OF TECHNOLOGY; WO2007/75427; (2007); A1;,
Highly efficient and robust molecular ruthenium catalysts for water oxidation
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Name is Benzylidenebis(tricyclohexylphosphine)dichlororuthenium, as a common heterocyclic compound, it belongs to ruthenium-catalysts compound, and cas is 172222-30-9, its synthesis route is as follows.

A suspension of 3.07 g (3.73 mmol) of [RuCl2(PCy3)2(phenylmethylene)] (commercial available from Sigma-Aldrich Inc., St. Louis, USA), 380 mg (3.84 mmol) copper chloride and 1.06 g (4.10 mmol) 4-chloro-2-trifluoromethyl-8-vinyl-quinoline in 135 ml methylene chloride was stirred at 300C for 90 min. The reaction mixture was evaporated to dryness and the isolated crude product purified by silica gel chromatography (hexane / ethyl acetat 2:1) and finally digested in 50 ml pentane at room temperature for 30 min to yield 429 mg (17percent) of the title compound as dark green crystals. MS: 697.0 (M+). 31P-NMR (121 MHz, C6D6): 54.2 ppm. 1H-NMR (300 MHz, C6D6): 1.18-2.35 (m, 30H); 2.60 (q, J=12.0Hz, 3H); 6.82 (t, J=6.0Hz, IH); 7.01 (d, J=3.0Hz, IH); 7.55 (d, J= 6.0Hz, IH); 7.89 (d, J=6.0Hz, IH); 17.80-17.90 (m, IH).

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Reference£º
Patent; F. HOFFMANN-LA ROCHE AG; WO2008/644; (2008); A1;,
Highly efficient and robust molecular ruthenium catalysts for water oxidation
Catalysts | Special Issue : Ruthenium Catalysts – MDPI