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A particularly flexible general way to synthesize 1-hydroxycycloalkene- 1-carboxylic-acid derivatives from 2-(tert-butyl)-2-methyl-1,3-dioxolan-4-one (1), a chiral equivalent of glycolic acid, is reported. The method is based on a double enolate alkylation of the glycolate derivative, followed by ring closing metathesis. A formal synthesis of (-)-quinic acid is reported to demonstrate the potential of this approach.

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

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The potent antibiotic ambruticin caused us to investigate two new aspects of cyclopropylboronic ester chemistry: we established the analytical basics for all 1,2,3-trisubstituted diastereoisomers as well as the cross-metathesis as a tool to synthesise vinylcyclopropylboronic esters.

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

Discovery of Benzylidenebis(tricyclohexylphosphine)dichlororuthenium

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A new amphiphilic AB2 star copolymer was synthesized by the combination of ring-opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP). Two different routes (methods A and B) were employed firstly to prepare the poly(oxanorbornene)-based monotelechelic polymers as the hydrophobic arm bearing dibromo-ended group via ROMP in the presence of two different terminating agents catalyzed by first generation Grubbs catalyst. The values of capping efficiency (CE) of the polymers were determined by NMR, which were 94% and 67% for methods A and B, respectively. Then, the dibromo-ended ROMP polymers were used as the macroinitiators for ATRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA) to produce two hydrophilic arms. The prepared amphiphilic AB2 star copolymers poly(7-oxanorborn-5-ene-exo,exo-2,3-dicarboxylic acid dimethyl ester)-block-bis[poly(2-(dimethylamino)ethyl methacrylate)] (PONBDMn-b-(PDMAEMAm)2) with a fixed chain length of hydrophobic PONBDM and various hydrophilic PDMAEMA chain lengths can self-assemble spontaneously in water to form polymeric micelles, which were characterized by dynamic light scattering, atom force microscopy, and transmission electron microscopy measurements.

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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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An efficient metal-catalyzed process that converts styrenyl ethers to 2-substituted chromenes is described. This class of reactions may be carried out on either terminal or disubstituted styrenyl substrates. Depending on the level of substitution of the olefins, the Ru-carbene catalyst may initiate reaction either by interaction with the styrenyl or the carbocyclic alkene. Metal-catalyzed rearrangements, carried out under an atmosphere of ethylene, afford excellent yields of monomeric products. With disubstituted styrene ethers, the presence of ethylene is also critical to reaction efficiency. Mechanistic data that rationalize these observations are provided. Although Ru complexes (PCy3)2Cl2Ru=CHCH=CPh2 or (PCy3)2Cl2Ru=CHPh effectively serve as catalysts, with the more functionalized substrates, higher yields are obtained when Mo(CHCMe2Ph)(N(2,6-(i-Pr)2C6H3))(OCMe(CF3)2)2 is used. A variety of starting materials for the metal-catalyzed chromene synthesis (disubstituted styrenes) are available in the optically pure form through the Zr-catalyzed kinetic resolution protocol, allowing several 2-substituted chromenes to be prepared in high enantiomeric purity. However, a number of functionalized substrates cannot be efficiently resolved by the latter method, indicating that more effective methods that address this deficiency are required.

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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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We present a comprehensive electronic structure analysis of structurally simple BN heterocycles using a combined UV-photoelectron spectroscopy (UV-PES)/computational chemistry approach. Gas-phase He I photoelectron spectra of 1,2-dihydro-1,2-azaborine 1, N-Me-1,2-BN-toluene 2, and N-Me-1,3-BN-toluene 3 have been recorded, assessed by density functional theory calculations, and compared with their corresponding carbonaceous analogues benzene and toluene. The first ionization energies of these BN heterocycles are in the order N-Me-1,3-BN-toluene 3 (8.0 eV) < N-Me-1,2-BN-toluene 2 (8.45 eV) < 1,2-dihydro-1,2-azaborine 1 (8.6 eV) < toluene (8.83 eV) < benzene (9.25 eV). The computationally determined molecular dipole moments are in the order 3 (4.577 D) > 2 (2.209 D) > 1 (2.154 D) > toluene (0.349 D) > benzene (0 D) and are consistent with experimental observations. The lambdamax in the UV-vis absorption spectra are in the order 3 (297 nm) > 2 (278 nm) > 1 (269 nm) > toluene (262 nm) > benzene (255 nm). We also establish that the measured anodic peak potentials and electrophilic aromatic substitution (EAS) reactivity of BN heterocycles 1-3 are consistent with the electronic structure description determined by the combined UV-PES/computational chemistry approach.

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

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Over the past decade conducting polymers have been studied for electronic applications, among them, molecular electronics: the study and investigation of molecular building blocks is a next-generation demanded area of research. Hence, the moletronic equivalent multi-functional advantages of cyclopolymerized 1,6-heptadiyne (HD) systems explored in this review. Further, this report elucidates physical properties via conditional cyclopolymerization methodologies, it describes the chemistry of tethering molecular-chains facilitated intrinsic-conductivity. HD and its derivatives induce superior conductivity characteristics via doping elements, wherein, significant electronic conductivity mechanism is attributable to the solitons and anti-solitons, which was described in this context. HD and their derivatives molecular mechanism, its compatibility are expounded for moletronic application, which is new insight of the article. Moreover, required inherent characteristics, for e.g., thermal-stability, chemical-resistance, mechanical properties, magnetic, and electronic properties have been discussed. Furthermore, failures, physical limitations, and its realizable similarity solutions for moletronics have described. Though electronic or moletronic components having failures and other physical limitations, HDs offers excellent conductivity with wide functional and physical properties that could lead to potential candidates to deliver efficient and low-cost moletronic devices.

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

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The deprotonation of 1,3-dimesitylbenzimidazolium tetrafluoroborate with a strong base afforded 1,3-dimesitylbenzimidazol-2-ylidene (BMes), which was further reacted in situ with rhodium or ruthenium complexes to afford three new organometallic products. The compounds [RhCl(COD)(BMes)] (COD is 1,5-cyclooctadiene) and cis-[RhCl(CO)2(BMes)] were used to probe the steric and electronic parameters of BMes. Comparison of the percentage of buried volume (%VBur) and of the Tolman electronic parameter (TEP) of BMes with those determined previously for 1,3-dimesitylimidazol-2-ylidene (IMes) and 1,3-dimesitylimidazolin-2-ylidene (SIMes) revealed that the three N-heterocyclic carbenes (NHCs) had very similar profiles. Nonetheless, changes in the hydrocarbon backbone subtly affected the stereoelectronic properties of these ligands. Accordingly, the corresponding [RuCl2(PCy 3)(NHC)(CHPh)] complexes displayed different catalytic behaviors in the ring-closing metathesis (RCM) of alpha,omega-dienes. In the benchmark cyclization of diethyl 2,2-diallylmalonate, the new [RuCl2(PCy 3)(BMes)(CHPh)] compound (1d) performed slightly better than the Grubbs second-generation catalyst (1a), which was in turn significantly more active than the related [RuCl2(PCy3)(IMes)(CHPh)] initiator (1b). For the formation of a model trisubstituted cycloolefin, complex 1d ranked in-between catalyst precursors 1a and 1b, whereas in the RCM of tetrasubstituted cycloalkenes it lost its catalytic efficiency much more rapidly.

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

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Clusters of O- and S-linked alpha-sialosides with valencies of two to four were constructed to serve as potential multivalent inhibitors towards sialoadhesins (siglecs). Thus, O- and S-prop-2-ynyl alpha-sialosides (3, 7), together with 4-iodophenyl sialoside 5 were prepared from acetochloroneuraminic acid derivative 1 using silver salicylate and propargyl alcohol for 3 and phase-transfer catalysis for 5 and 7, respectively. Oxidative acetylenic homocoupling of 3 and 7 under Glaser conditions (CuCl, O2) provided 1,3-diynes 8 and 9 in 83-86% yields. Palladium catalyzed cross-coupling of O-prop-2-ynyl sialoside 3 with 5 using Pd2(dba)3 and PPh3 gave nonsymmetrical dimer 10 (82%). Alternatively, symmetrical clusters were then prepared as above under Sonogashira cross-coupling conditions with 1,4-diiodobenzene (11), 1,3,5-triodobenzene (14), and finally 1,2,4,6-tetraiodobenzene (17) to provide both O- and S-linked dimers 12 (93%) and 13 (88%), trimers 15 (81%) and 16 (76%), while only O-linked tetramer 18 was prepared in 87% yield. Finally, treatment of the O-linked prop-2-ynyl sialoside 3 with Grubbs’ metathesis catalyst Cl2Ru(PCy3)2=CHPh (19) gave, as expected, benzeneannulation regioisomeric trimers 20a, 20b in 68% yield.

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

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This disclosure relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by an olefin metathesis catalyst. According to one aspect, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting, in the presence of a ruthenium alkylidene metathesis catalyst, an olefinic substrate comprised of at least one internal olefin with a cross metathesis partner comprised of an alpha olefinic reactant, under reaction conditions effective to allow cross-metathesis to occur, wherein the reaction conditions include a reaction temperature of at least 35 C. The methods, compositions, reactions and reaction systems herein disclosed have utility in the fields of catalysis, organic synthesis, and industrial chemistry.

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

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A fruitful combination of molecular dynamics based design and modern synthetic reactions led to a conformatively rigidized cis-peptidyl proline surrogate (see picture). NMR spectroscopic experiments clearly show the existance of type VIa beta-turn properties that are of interest in drug discovery.

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