Top Picks: new discover of (1R,2R)-N1,N1,N2,N2-Tetramethylcyclohexane-1,2-diamine

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Lithiated aryl carbamates (ArLi) bearing methoxy or fluoro substituents in the meta position are generated from lithium diisopropylamide (LDA) in THF, n-BuOMe, Me2NEt, dimethoxyethane (DME), N,N,N?,N?- tetramethylethylenediamine (TMEDA), N,N,N?,N?- tetramethylcyclohexanediamine (TMCDA), and hexamethylphosphoramide (HMPA). The aryllithiums are shown with 6Li, 13C, and 15N NMR spectroscopies to be monomers, ArLi-LDA mixed dimers, and ArLi-LDA mixed trimers, depending on the choice of solvent. Subsequent Snieckus-Fries rearrangements afford ArOLi-LDA mixed dimers and trimers of the resulting phenolates. Rate studies of the rearrangement implicate mechanisms based on monomers, mixed dimers, and mixed trimers.

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Extending the class of group 6 metal-metal bonded methylate compounds supported by alkali metal counter-ions, the first sodium octamethylmolybdate(ii) complex [(TMEDA)Na]4Mo2Me8 and heptamethylchromate(ii) relations [(donor)Na]3Cr2Me7 (donor is TMEDA or TMCDA) are reported. The former was made by treating [(Et2O)Li]4Mo2Me8 with four equivalents of NaOtBu/TMEDA in ether; whereas the latter resulted from introducing TMEDA or TMCDA to ether solutions of octamethyldichromate [(Et2O)Na]4Cr2Me8. X-ray crystallography revealed [(TMEDA)Na]4Mo2Me8 is dimeric with square pyramidal Mo centres [including a short Mo-Mo interaction of 2.1403(3) A] each with four methyl groups in a mutually eclipsed conformation. In dinuclear [(TMCDA)Na]3Cr2Me7 trigonal bi-pyramidal Cr centres each bond to three terminal methyl groups and one common Me bridge, that produces a strikingly short Cr-Cr contact of 1.9136(4) A. Broken symmetry density functional theoretical calculations expose the multiconfigurational metal-metal bonding in these compounds with a Mo-Mo bond order of 3 computed for octamethylmolybdate(ii). This is contrasted by the single Cr-Cr bond in heptamethylchromate(ii) where the singlet ground state is derived by strong antiferromagnetic coupling between adjacent metal ions.

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Reacting cesium fluoride with an equimolar n-hexane solution of lithium bis(trimethylsilyl)amide (LiHMDS) allows the isolation of CsHMDS (1) in 80% yield (after sublimation). This preparative route to 1 negates the need for pyrophoric Cs metal or organocesium reagents in its synthesis. If a 2:1 LiHMDS:CsF ratio is employed, the heterobimetallic polymer [LiCs(HMDS)2]? 2 was isolated (57% yield). By combining equimolar quantities of NaHMDS and CsHMDS in hexane/toluene [toluene·NaCs(HMDS)]? 3 was isolated (62% yield). Attempts to prepare the corresponding potassium-cesium amide failed and instead yielded the known monometallic polymer [toluene·Cs(HMDS)]? 4. With the aim of expanding the structural diversity of Cs(HMDS) species, 1 was reacted with several different Lewis basic donor molecules of varying denticity, namely, (R,R)-N,N,N’,N’-tetramethylcyclohexane-1,2-diamine [(R,R)-TMCDA] and N,N,N’,N’-tetramethylethylenediamine (TMEDA), N,N,N’,N’,N’-pentamethyldiethylenetriamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (Me6-TREN) and tris[2-(2-methoxyethoxy)ethyl]amine (TMEEA). These reactions yielded dimeric [donor·NaCs(HMDS)2]2 5-7 [where donor is (R,R)-TMCDA, TMEDA and PMDETA respectively], the tetranuclear “open”-dimer [{Me6-TREN·Cs(HMDS)}2{Cs(HMDS)}2] 8 and the monomeric [TMEEA·Cs(HMDS)] 9. Complexes 2, 3, and 5-9 were characterized by X-ray crystallography and in solution by multinuclear NMR spectroscopy.

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Chiral Catalysts,
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Alkyllithium compounds are not generally stable at room temperature, therefore strategies were established to overcome this limitation. We present a systematic approach to obtain a stereochemically enriched benzyllithium compound, starting with the simple addition of a chiral auxiliary and ending by incorporation of the auxiliary in the substrate. Thereby, a very unusual dimer of a lithiated benzylsilane was obtained, which could be split into stereochemically enriched monomers by the addition of Lewis bases. Furthermore, we were able to understand the factors responsible for this stereochemical enrichment by using quantum chemical calculations and clarify the configuration of the lithiated compound and the corresponding trapping product by crystallisation. This enabled us to determine the stereochemical course of the deprotonation and the subsequent metathesis reaction.

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Chiral Catalysts,
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(Chemical Equation Presented) The alpha-lithiation of amines by direct deprotonation has to date only been possible in a few systems. The enantiomerically pure amine (R,R)-TMCDA coordinates to tBuLi to form a monomeric molecular structure. Starting from tBuLi-(R,R)-TMCDA, lithiation of the ligand occurs, which results in a trimeric alpha-lithiated amine (see picture).

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Chiral Catalysts,
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When n-hexane solutions of an excess of sodium bis(trimethylsilyl)amide (NaHMDS) are combined with cesium halide (halide = Cl, Br, or I) in the presence of the tetradentate donor molecule [tris[2-(dimethylamino)ethyl]amine] (Me6TREN), the isolation and characterization of a series of sodium amide/sodium halide mixed aggregates was forthcoming. Cesium halide was employed because it efficiently reacted with NaHMDS to produce a molecular, soluble source of sodium halide salt (which was subsequently captured by an excess of NaHMDS) via a methathetical reaction. These mixed sodium amide/sodium halide complexes are formally sodium sodiates, are deficient in halide with respect to the amide, and have the general formula [{Na5(mu-HMDS)5(mu5-X)}{Na(Me6TREN)}] [where X = Cl (1), Br (2), or I (3)]. The influence of the donor ligand was studied for the NaI/NaHMDS system, and when n-hexane solutions of this composition were treated with tridentate donors such as N,N,N?,?,?-pentamethyldiethylenetriamine (PMDETA) or N,N,N?,N?-tetramethyldiaminoethyl ether (TMDAE), solvent-separated ion-pair cocomplexes [Na5(mu-HMDS)5(mu5-I)]'[Na3(mu-HMDS)2(PMDETA)2]+ (4) and [Na5(mu-HMDS)5(mu5-I)]'[Na(TMDAE)2]+ (5) were isolated. However, upon reaction with bidentate proligands such as the chiral diamine (R,R)-N,N,N?,N?-tetramethylcyclohexane-1,2-diamine [(R,R)-TMCDA] or N,N,N?,N?-tetramethylethylenediamine (TMEDA), neutral complexes [Na4(mu-HMDS)3(mu4-I)(donor)2] [donor = (R,R)-TMCDA (6) and TMEDA (7)] were produced. To illustrate the generality of the latter reaction with other halides, [Na4(mu-HMDS)3(mu4-Br)(TMEDA)2] (8) was also prepared by employing NaBr in the synthesis instead of NaI.

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Chiral Catalysts,
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Several Lewis base adducts of the synthetically important lithium tris(n-butyl)magnesiate LiMg(nBu)3 have been prepared and structurally characterised. The complexes were prepared by a co-complexation approach i.e., by combining the monometallic nBuLi and nBu2Mg reagents in hydrocarbon solution before adding a molar equivalent of a donor molecule (a bidentate amine, tridentate amine or cyclic ether). The lithium magnesiates all adopt variants of the “Weiss motif” structure, i.e., contacted ion pair dimers with a linear arrangement and metals connected by butyl anions, where tetrahedral magnesium ions are in the central positions and the lithiums occupy the outer region, solvated by a neutral Lewis donor [(donor)Li(mu-nBu)2Mg(mu-nBu)2Mg(mu-nBu)2Li(donor)]. When TMPDA, PMDETA or (R,R)-TMCDA [TMPDA = N,N,N?N?-tetramethylpropanediamine; PMDETA = N,N,N?,N?,N?-pentamethyldiethylenetriamine; and (R,R)-TMCDA = (R,R)-N,N,N?,N?-tetramethylcyclohexane-1,2-diamine], are employed, dimeric tetranuclear lithium magnesiates are produced. Due to the tridentate nature of the ligand, the PMDETA-containing structure (2) has an unusual ‘open’-motif. When TMEDA (TMEDA = N,N,N?,N?-tetramethylethylenediamine) is employed, a n-butoxide-containing complex [(TMEDA)Li(mu-nBu)(mu-OnBu)Mg2(nBu)2(mu-nBu)(mu-OnBu)Li(donor)] has been serendipitously prepared and adopts a ladder conformation which is commonly observed in lithium amide chemistry. This complex has also been prepared using a rational methodology. When 1,4-dioxane is employed, the donor stitches together a polymeric array of tetranuclear dimeric units (6). The hydrocarbon solution structures of the compounds have been characterised by 1H, 7Li, 13C NMR spectroscopy; 2 has been studied by variable temperature and DOSY NMR.

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Dimethylphenylphosphine borane is readily deprotonated at both methyl groups with tBuLi and (R,R)-TMCDA to the corresponding dilithiated Lewis base adduct, featuring an intriguing structural motif with stabilising Li-H interactions.

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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. 53152-69-5, Name is (1R,2R)-N1,N1,N2,N2-Tetramethylcyclohexane-1,2-diamine, molecular formula is C10H22N2. In a Article,once mentioned of 53152-69-5, Application In Synthesis of (1R,2R)-N1,N1,N2,N2-Tetramethylcyclohexane-1,2-diamine

We herein present the synthesis and crystallographic characterisation of lithium silylamides displaying different coordination numbers and aggregation states according to the number of N- and O-donor functions in the starting material, (aminomethyl) substituted silazane ligands. The dimeric dimethyl-(N-lithio-tert-butylamino)-piperidinomethyl)-silane and dimethyl-(N-lithio-iso-propylamino)-piperidinomethyl)-silane, with three-coordinate lithium centres, were prepared by deprotonation of the corresponding silazane with nBuLi. Using the tridentate silazane (1R,2R)-N1-[{(tert-butylamino)-dimethylsilyl}methyl]-N 1,N2,N2-trimethylcyclohexane-1,2-diamine a mixed “dimer” of lithium silylamide and lithium silanolate with four-coordinate lithium centres was obtained. Additionally, a monomeric lithium silylamide was synthesised using the tridentate [bis(methoxyethyl)aminomethyl] side arm.

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Chiral Catalysts,
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53152-69-5, Name is (1R,2R)-N1,N1,N2,N2-Tetramethylcyclohexane-1,2-diamine, molecular formula is C10H22N2, belongs to chiral-catalyst compound, is a common compound. In a patnet, once mentioned the new application about 53152-69-5, Product Details of 53152-69-5

The preparation of aminomethyl functionalised silanes based on the alpha-lithiated amine, (1R,2R)-N,N,N?,N?-tetramethylcyclohexane-1, 2-diamine [(R,R)-TMCDA] is reported. This methodology can be applied for the synthesis of mono-aminomethyl substituted systems, but most remarkably also for di- and trifunctionalised compounds. The trapping of the lithiated amine is accompanied by transmetallation reactions resulting in the formation of (silylmethyl)silanes depending on the reaction temperature. The zinc(ii) halide complexes of the mono-functionalised systems show the formation of exclusively one configuration of the stereogenic nitrogen atom, in which the spatially more demanding substituent exhibits the pseudo-equatorial position. The di- and trifunctionalised systems feature high sensitivity towards Si-C bond cleavage under re-formation of the (R,R)-TMCDA fragment. The Royal Society of Chemistry 2012.

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Chiral Catalysts,
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