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Alkene metatheses in transition metal coordination spheres: Dimacrocyclizations that join trans positions of square-planar platinum complexes to give topologically novel diphosphine ligands

The alkene-containing phosphines PPh((CH2)nCH=CH 2)2)2 (4) are prepared from PPhH2, n-BuLi, and the corresponding bromoalkenes (1: 2 : 2), and combined with the platinum tetrahydrothiophene complex [Pt(mu-Cl)(C6F 5)(S(CH2CH2-)2)]2 (12) to give the square-planar adducts trans-(Cl)(C6F5) Pt(PPh((CH2)nCH=CH2)2)2 (11, 93-73%; n = a, 2; b, 3; c, 4; d, 5; e, 6; f, 8). Ring-closing metatheses with Grubbs’ catalyst (2) are studied. With 11e, two isomers of trans-(Cl)(C6F5)Pt(PPh(CH2) 14P(CH2)14Ph) (15e) are isolated after hydrogenation. Both form via dimacrocyclization between the trans-phosphine ligands, but differ in the dispositions of the PPh rings (syn, 31%; anti, 7%). The alternative intraligand metathesis product trans-(Cl)(C6F 5)Pt(PPh(CH2)14)2 (16e) is independently prepared by (i) protecting 4e as a borane adduct, H 3B¡¤PPh((CH2)6CH=CH2) 2, (ii) cyclization with 2 and hydrogenation to give H 3B¡¤PPh(CH2)14, (iii) deprotection and reaction with 12. The sample derived from lie contains ?2% 16e; mass spectra suggest that the other products are dimers or oligomers. The structures of syn-15e, anti-15e and 16e are verified crystallographically, and the macrocycle conformations analyzed. As expected from the (CH2)n segment length, 11a undergoes intraligand metathesis to give (Z,Z)-trans-(Cl)(C6F5)Pt(PPh(CH2) 2CH=CH(CH2)2)2 (86%), as confirmed by a crystal structure of the hydrogenation product. Although lib does not yield tractable products, 11c gives syn-(E,E)-trans-(Cl)(C6F 5)Pt(PPh(CH2)4CH=CH(CH2) 4P(CH2)4CH=CH(CH2)4Ph) (21%). This structure, and that of the hydrogenation product (syn-15c; 95%), are verified crystallographically. Analogous sequences with 11d,f give syn-15d,f (5 and 14% overall).

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.172222-30-9, Name is Benzylidenebis(tricyclohexylphosphine)dichlororuthenium, molecular formula is C43H72Cl2P2Ru. In a Article£¬once mentioned of 172222-30-9, name: Benzylidenebis(tricyclohexylphosphine)dichlororuthenium

Total syntheses of (+)-ricinelaidic acid lactone and of (-)-gloeosporone based on transition-metal-catalyzed C-C bond formations

Total syntheses of the macrolides (R)-(+)-ricinelaidic acid lactone (6) and (-)-gloeosporone (7), a fungal germination self-inhibitor, are presented, which are distinctly shorter and more efficient than any of the previous approaches to these targets reported in the literature. Both of them benefit from the remarkable ease of macrocyclization of 1,omega-dienes by means of ring-closing olefin metathesis (RCM) using the ruthenium carbene 1a as catalyst precursor. The diene substrates are readily formed via the enantioselective addition of dialkylzinc reagents to aldehydes in the presence of catalytic amounts of Ti(OiPr)4 and bis-triflamide 18 and/or the stereoselective allylation of aldehydes developed by Keck et al. using allyltributylstannane in combination with a catalyst formed from Ti(OiPr)4 and (S)(-)-1,1′-bi-2-naphthol. Comparative studies show this latter procedure to be more practical than the stoichiometric allylation reaction employing the allyltitanium-alpha,alpha,alpha’,alpha’-tetraaryl-1,3-dioxolane-4,5-dimethanol complex 3b. Finally, a method for the efficient ring closure of 4-pentenoic acid esters by RCM is presented that relies on the joint use of 1a and Ti(OiPr)4 as a binary catalyst system. These results not only expand the scope of RCM to previously unreactive substrates but also provide additional evidence for the important role of ligation of the evolving ruthenium carbene center to a polar relay substituent on the substrate which constitutes the necessary internal bias for the RCM-based macrocyclization process.

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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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A flexible and unified strategy for syntheses of cladospolides A, B, C, and iso-cladospolide B

A simple, efficient and flexible strategy for the syntheses of cladospolides A-C and iso-cladospolide B is reported here. This strategy involves Julia-Kocienski olefination and Yamaguchi macrolactonization as key steps, starting from either d-ribose or suitable tartaric acid esters. Although our initial efforts towards cladospolide A involving a ring closing metathetic approach were not successful, changing the mode of ring closure and the use of Julia-Kocienski olefination for the construction of the key intermediate solved this issue and paved the way for the completion of total syntheses of this class of natural products.

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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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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Article£¬once mentioned of 246047-72-3, Safety of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

delta,epsilon-unsaturated alpha,beta-diamino acids as building blocks for the asymmetric synthesis of diverse alpha,beta-diamino acids

A building block approach for the synthesis of ¡À,beta-diamino acids is described, which involves the diastereodivergent preparation of two sets of orthogonally protected delta,epsilon-unsaturated ¡À,beta-diamino acids as templates for the preparation of 12 new ¡Àbeta-diamino acids of biological relevance using simple techniques.

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.Safety of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 246047-72-3, in my other articles.

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

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Evaluating transition-metal-catalyzed transformations for the synthesis of laulimalide

(Chemical Equation Presented) Laulimalide is a structurally unique 20-membered marine macrolide displaying microtubule stabilizing activity similar to that of paclitaxel and the epothilones. The use of atom-economical transformations such as a Rh-catalyzed cycloisomerization to form the endocyclic dihydropyran, a dinuclear Zn-catalyzed asymmetric glycolate aldol reaction to prepare the syn 1,2-diol, and an intramolecular Ru-catalyzed alkene-alkyne coupling to build the macrocycle enabled us to synthesize laulimalide via an efficient and convergent pathway. The designed synthetic route also allowed us to prepare an analogue of the natural product that possesses significant cytotoxic activity.

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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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From vinyl pyranoses to carbasugars by an iron-catalyzed reaction complementary to classical Ferrier carbocyclization

Starting from vinyl pyranoses an iron-catalyzed tandem isomerization- intramolecular aldolization reaction was developed to prepare cyclohexenone derivatives bearing substituents on the double bond, and it has been applied in a short synthesis of 4-epi-gabosines A and B, from d-glucose. The Royal Society of Chemistry 2009.

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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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Total synthesis and structural elucidation of azaspiracid-1. Final assignment and total synthesis of the correct structure of azaspiracid-1

The molecular structure of azaspiracid-1, a neurotoxin isolated from mussels, has been elucidated by total synthesis which also enriched its supplies. The degradatively derived fragments of this marine biotoxin, compounds 5 (EFGHI), 6 (FGHI), and 40 (ABCD), were matched with synthetic materials, thus confirming their structural identities. Based on this detective work, a new structure of azaspiracid-1 (i.e., 1) was proposed and constructed by total synthesis. The final strategy for the total synthesis of azaspiracid-1 featured a dithiane anion (C21-C27 fragment) reacting with a pentafluorophenol ester (C1-C20 fragment) followed by a Stille-type union of an advanced allylic acetate substrate (C1-C 27 fragment) with a vinyl stannane as the main coupling processes to assemble the carbon skeleton of the molecule. In addition to the total synthesis of azaspiracid-1 (1), the syntheses of its C1-C20 epimer (2) and of several truncated analogues for biological investigations are described.

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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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Synthesis of Various Heterocycles Having a Dienamide Moiety by Ring-Closing Metathesis of Ene-ynamides

Ring-closing metathesis (RCM) of ynamides, having alkene substituents of various lengths on the side chain, was demonstrated using the second-generation Grubbs catalyst. When the reaction of ene-ynamides was carried out in the presence of 5 mol% of the catalyst, RCM proceeded smoothly to give quinoline or isoquinoline derivatives having a dienamide unit in good yields. Furthermore, RCM of ene-ynamides, having one more carbon on the side chain, proceeded smoothly to provide seven-membered heterocycles having a dienamide component. Similarly, eight-membered heterocycles, diazocine and benzodiazocine, were also synthesized by RCM of ene-ynamides in good yields.

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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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Synthesis, Structure, and Local Molecular Dynamics for Crystalline Rotors Based on Hecogenin/Botogenin Steroidal Frameworks

The synthesis and solid-state characterization of a series of cyclic/acyclic molecular rotors derived from naturally occurring steroidal 12-oxosapogenins are described. The bridged molecular rotors with rigid steroidal frameworks were obtained by employing ring-closing metathesis (RCM) as a key step. The X-ray diffraction technique was employed for determination and refinement of the crystal and molecular structure of selected models giving good quality single crystals. In the case of the bridged hecogenin molecular rotor 11E for which poor quality crystals were obtained, an NMR crystallography approach was used for fine refinement of the structure. Solid state NMR spectroscopic techniques were applied for the study of local molecular dynamics of the featured acyclic/cyclic molecular rotors. Analysis of 13C principal components of chemical shift tensors and chemical shift anisotropy (CSA) as well as heteronuclear 1H-13C dipolar couplings (DC) unambiguously proved that aromatic rings located in the space within the rigid steroidal framework both for cyclic and acyclic rotors are under kHz exchange regime. Experimental results were confirmed by theoretical calculations of rotation barrier on the density functional theory level. Small distinctions in the values of CSA and DC for the rotors under investigation are explained on the basis of differences in their molecular structures.

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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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Asymmetric Allylation/RCM-Mediated Synthesis of Fluorinated Benzo-Fused Bicyclic Homoallylic Amines As Dihydronaphthalene Derivatives

Enantiomerically enriched fluorinated benzo-fused bicyclic homoallylic amines have been synthesized through an asymmetric allylation/ring closing metathesis (RCM) sequence. This sequence has been carried out using alpha-trifluoromethylstyrene derivatives as key intermediates, synthesized by microwave radiation. The great deactivating effect exerted by such substituents has been brought to light by a comparative study.

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