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The reactions of allenylphosphonates/allenylphosphine oxides or an allenyl sulfone [4-Cl-C6H4-SO2C(R)=C=CMe2] with the aldimine PhCH=NTs in the presence of a carbene [NHC·HCl/DBU] afford tosylated allylic phosphonates/phosphine oxides or a sulfone. This reaction involves C-S bond formation and not C-O bond formation, and thus is different from similar reactions of allenes with PhCH=NTs in the presence of bases like DMAP, DBU or Ph3P/(alkyl)3P wherein cycloaddition products are generally observed. The reactions of phosphorylated allenes with DBU lead to the unprecedented formation of products in which the DBU ring is cleaved, as evidenced by single crystal X-ray crystallography. This observation suggests a ?reactant? role for DBU when using this base in the reactions of allenes.

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A cationic phosphoranide featuring a normal and an abnormal imidazoliumyl substituent was prepared through the reaction of a P-centered cation with an N-heterocyclic carbene (NHC). The remarkable reactivity of this compound allows the formation of two- or three-coordinate P-centered cations, illustrating the ability of imidazoliumyl substituents to stabilize high- and low-coordinated P atoms. Copyright

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Even though the Dewar-Chatt-Duncanson model has been successfully used by chemists since the 1950s, no experimental methodology is yet known to unambiguously estimate the constituents (donation and back-donation) of a metal-ligand interaction. It is demonstrated here that one of these components, the metal-to-ligand pi back-donation, can be effectively probed by NMR measurements aimed at determining the rotational barrier of a C – N bond (DeltaHr? ) of a nitrogen acyclic carbene ligand. A large series of gold(I) complexes have been synthesized and analyzed, and it was found that the above experimental observables show an accurate correlation with back-donation, as defined theoretically by the appropriate charge displacement originated upon bond formation. The proposed method is potentially of wide applicability for analyzing the ligand effect in metal catalysts and guiding their design.

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The system, Pd(OAc)2/imidazolium salts (L2), was found as an efficient catalyst in the Heck coupling reaction of olefins with aryl halides and Suzuki reactions of various aryl halides with aryl boronic acids under aerobic condition. This catalytic system demonstrates great tolerance to a wide range of groups on all substrates of aryl halides, alkenes and aryl boronic acids.

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Chiral Catalysts,
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A user-friendly and general mechanochemical method was developed to access rarely described NHC (N-heterocyclic carbene) silver(i) complexes featuring N,N-diarylimidazol(idin)ene ligands and non-coordinating tetrafluoroborate or hexafluorophosphate counter anions. Comparison with syntheses in solution clearly demonstrated the superiority of the ball-milling conditions.

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Chiral Catalysts,
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The anionic N-heterocyclic dicarbenes (NHDCs) I are demonstrated to be a convenient platform from which abnormal NHC (aNHC)-borane complexes V-VII may be prepared. The anionic NHDC binuclear complex II and the aNHC mononuclear adduct VII can be interconverted through lithiation and protonation, respectively, of the C2 carbon atom of the imidazole ring.

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Chiral Catalysts,
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In an article, published in an article, once mentioned the application of 250285-32-6, Name is 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride,molecular formula is C27H37ClN2, is a conventional compound. this article was the specific content is as follows.Quality Control of: 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride

A process for preparing a N-phenylisoxazolidin-5-one derivative is provided. The process for preparing the N-phenylisoxazolidin-5-one derivative comprises reacting an alpha, beta-unsaturated aldehyde with nitrosobenzene in the presence of a N-heterocyclic carbene (NHC) catalyst. A process for preparing an N-alkoxyphenyl protected beta-amino acid ester derivative is further provided. The process for preparing the N-alkoxyphenyl protected beta-amino acid ester derivative comprises reacting an alpha, beta-unsaturated aldehyde with nitrosobenzene in the presence of a N-heterocyclic carbene (NHC) catalyst to form a N-phenylisoxazolidin-5-one derivative, and then treating the N-phenylisoxazolidin-5-one derivative with an alcohol in the presence of an acid catalyst. A process for preparing an N-alkoxyphenyl protected beta-amino acid ester derivative, comprising treating a N-phenylisoxazolidin-5-one derivative with an alcohol in the presence of an acid catalyst, is also provided.

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Chiral Catalysts,
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A series of heteroleptic three-coordinate Cu(i) complexes bearing monodentate N-heterocyclic carbene (NHC) ligands of the type 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) and 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr), and bidentate N-donor ligands of the type unsymmetrically-substituted dimethyl dipyridylamine (Me2Hdpa) and bis(mesityl)biazanaphthenequinone (mesBIAN) have been synthesized. The complexes [Cu(IPr)(3,4?-Me2Hdpa)]PF6, 1; [Cu(IPr)(3,5?-Me2Hdpa)]PF6, 2; [Cu(IPr)(3,6?-Me2Hdpa)]PF6, 3; [Cu(IPr)(mesBIAN)]PF6, 6; [Cu(SIPr)(3,4?-Me2Hdpa)]PF6, 7; [Cu(SIPr)(3,5?-Me2Hdpa)]PF6, 8; and [Cu(SIPr)(3,3?-Me2Hdpa)]PF6, 11 have been characterized by 1H and 13C NMR spectroscopies, elemental analysis, cyclic voltammetry, and photophysical studies in solid and solution phase. Single crystal X-ray structures were obtained for all complexes except 11. The crystallographic data reveal a mononuclear structure for all complexes with the copper atom ligated by one C and two N atoms. The UV-Vis absorption spectra of all dipyridylamine complexes in CH2Cl2 show a strong ligand-centered absorption band around 250 nm and a strong metal-to-ligand charge transfer (MLCT) band around 300 nm. When irradiated with UV light, the complexes exhibit strong emission maxima at 453-482 nm with photoluminescence quantum yields (PLQY) ranging from 0.21 to 0.87 in solid state. While the PLQY values are comparable to those of the symmetrical [Cu(IPr)(Me2Hdpa)]PF6 complexes, a stabilizing CH-pi interaction has been reduced in the current systems. In particular, complex 3 lacks any strong CH-pi interaction, but emits more efficiently than 1 and 2 wherein the interactions exist. Structural data analysis was performed to clarify the role of ligands’ plane angle and the NH/CH?F interactions to the observed light interaction of unsymmetrical [Cu(NHC)(Me2Hdpa)]PF6 complexes. DFT calculations were performed to assist in the assignment of the electronic structure and excited state behavior of the complexes.

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By using an N-heterocyclic carbene catalyst bearing a hydroxyl moiety, the asymmetric formal (3 + 2) cyclization of aryl 3-bromoenals and isatins was achieved to produce a series of chiral spirooxindole-butenolides including an alkenyl-substituted compound, which underwent benzannulations with benzynes to form intriguing spirocyclic scaffolds.

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The behavior of ubiquitously used nickel, palladium, and platinum complexes containing N-heterocyclic carbene ligands was studied in solution in the presence of aliphatic amines. Transformation of M(NHC)X2L complexes readily occurred according to the following reactions: (i) release of the NHC ligand in the form of azolium salt and formation of metal clusters or nanoparticles and (ii) isomerization of mono-NHC complexes M(NHC)X2L to bis-NHC derivatives M(NHC)2X2. Facile cleavage of the M-NHC bond was observed and provided the possibility for fast release of catalytically active NHC-free metal species. Bis-NHC metal complexes M(NHC)2X2 were found to be significantly more stable and represented a molecular reservoir of catalytically active species. Slow decomposition of the bis-NHC complexes by removal of the NHC ligands (also in the form of azolium salts) occurred, generating metal clusters or nanoparticles. The observed combination of dual fast- and slow-release channels is an intrinsic latent opportunity of M/NHC complexes, which balances the activity and durability of a catalytic system. The fast release of catalytically active species from M(NHC)X2L complexes can rapidly initiate catalytic transformation, while the slow release of catalytically active species from M(NHC)2X2 complexes can compensate for degradation of catalytically active species and help to maintain a reliable amount of catalyst. The study clearly shows an outstanding potential of dynamic catalytic systems, where the key roles are played by the lability of the M-NHC framework rather than its stability.

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Reference:
Chiral Catalysts,
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