26902-54-5

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• 6852-58-0 N-benzylidene tert-butylamine 
• 917-54-4 methyllithium 
• 102564-44-3 N-tert-Butyl-N-(1-phenylethyl)hydroxylamine 
• 40475-58-9 1,1-dimethyl-n-(1-phenylethylidene)ethanamine 
• 100-41-4 ethylbenzene 
• 100-52-7 benzaldehyde 
• 594-19-4 tert.-butyl lithium 
• 103794-57-6 (R)-O-methyl-N-(α-methylbenzyl)hydroxylamine 
• 585-71-7 (1-bromoethyl)benzne 
• 75-64-9 tert-butylamine 

Downstream Products

• 628729-63-5 α-bromoacetyl-N-(tert-butyl)-N-(α-phenylethyl)amide 

Relevant academic research and scientific papers

Metallic Barium: A Versatile and Efficient Hydrogenation Catalyst

Ba metal was activated by evaporation and cocondensation with heptane. This black powder is a highly active hydrogenation catalyst for the reduction of a variety of unactivated (non-conjugated) mono-, di- and tri-substituted alkenes, tetraphenylethylene, benzene, a number of polycyclic aromatic hydrocarbons, aldimines, ketimines and various pyridines. The performance of metallic Ba in hydrogenation catalysis tops that of the hitherto most active molecular group 2 metal catalysts. Depending on the substrate, two different catalytic cycles are proposed. A: a classical metal hydride cycle and B: the Ba metal cycle. The latter is proposed for substrates that are easily reduced by Ba0, that is, conjugated alkenes, alkynes, annulated rings, imines and pyridines. In addition, a mechanism in which Ba0 and BaH2 are both essential is discussed. DFT calculations on benzene hydrogenation with a simple model system (Ba/BaH2) confirm that the presence of metallic Ba has an accelerating effect.

Alkaline Earth Metal Aluminates as Catalysts for Imine Hydrogenation

Alkaline earth (Ae) metal complexes with the alanate anion AlH4-have been prepared by salt metathesis between NaAlH4and AeCl2in THF and could be isolated as Mg(AlH4)2·(THF)4, Ca(AlH4)2·(THF)4, and Sr(AlH4)2·(THF)5. The previously reported crystal structure of the Mg alanate complex shows bonding of AlH4-with one bridging hydride, H3Al-(μ-H)-Mg, while the Ca and Sr alanates show a combination of H3Al-(μ-H)-Ae and H2Al-(μ-H)2-Ae bridging. The heteroleptic β-diketiminate complexes (DIPPBDI)Mg(AlH4)·THF and (DIPPBDI)Ca(AlH4)·(THF)2have been prepared by reaction of the corresponding Ae hydride complexes with AlH3·(THF)2[DIPPBDI = DIPP-NC(Me)C(H)C(Me)N-DIPP, where DIPP = 2,6-diisopropylphenyl]. Crystal structures show H2Al-(μ-H)2-Ae bridging. The Ca complex decomposes at room temperature by reduction of the β-diketiminate anion. Density functional theory calculations (B3PW91/def2tzvpp) show that the formation of Ae(AlH4)2from AeH2and AlH3is exothermic by δH (kilocalories per mole): Be, -68.8; Mg, -66.1; Ca, -95.4; Sr, -100.9; Ba, -112.3. Calculations of NPA charges on LiAlH4and the Ae alanate complexes (Ae = Mg, Ca, or Sr) show that these are highly ionic salts in which the charge on AlH4-of approximately -0.95 is hardly dependent on the countercation. Compared to LiAlH4, the Ae alanates are very efficient catalysts for imine hydrogenation, clearly extending the substrate scope. In addition to aldimines RC(H)=NR′ (R/R′ = Ph/tBu, tBu/tBu, nPr/tBu, or Ph/Ph), ketimine PhC(Me)=NtBu could be reduced. The salt [Bu4N+][AlH4-] is catalytically not active, which shows that the s-block metal is crucial. The highest activities were found for the heterobimetallic Ca and Sr alanates.

The Chemistry of a Non-Interacting Vicinal Frustrated Phosphane/Borane Lewis Pair

The dimesitylphosphinocyclopentene/HB(C6F5)2-derived vicinal trans-1,2-P/B frustrated Lewis pair (FLP) 4 shows no direct phosphane–borane interaction. Toward some reagents it behaves similar to an intermolecular FLP; it cleaves dihydrogen, deprotonates terminal alkynes, and adds to organic carbonyl compounds including CO2. It shows typical intramolecular FLP reaction modes (cooperative 1,1-additions) to mesityl azide, to carbon monoxide, and to NO. The latter reaction yields a persistent P/B FLPNO nitroxide radical, which undergoes H-atom abstraction reactions. The FLP 4 serves as a template for the CO reduction by [HB(C6F5)2] to generate a FLP-η2-formylborane. The formylborane moiety is removed from the FLP template by reaction with pyridine to yield a genuine pyridine stabilized formylborane that undergoes characteristic borane carbaldehyde reactions (Wittig olefination, imine formation). Most new products were characterized by X-ray diffraction.

REACTIONS OF STANNYL CATIONS

The present invention relates to a method of reducing, cleaving and/or coupling at least one C=O, C-O, C=C or C=N bond of a compound, using a reagent comprising a stannyl cation.

Versatile Catalytic Hydrogenation Using A Simple Tin(IV) Lewis Acid

Despite the rapid development of frustrated Lewis pair (FLP) chemistry over the last ten years, its application in catalytic hydrogenations remains dependent on a narrow family of structurally similar early main-group Lewis acids (LAs), inevitably placing limitations on reactivity, sensitivity and substrate scope. Herein we describe the FLP-mediated H2activation and catalytic hydrogenation activity of the alternative LA iPr3SnOTf, which acts as a surrogate for the trialkylstannylium ion iPr3Sn+, and is rapidly and easily prepared from simple, inexpensive starting materials. This highly thermally robust LA is found to be competent in the hydrogenation of a number of different unsaturated functional groups (which is unique to date for main-group FLP LAs not based on boron), and also displays a remarkable tolerance to moisture.

Exploiting Deep Eutectic Solvents and Organolithium Reagent Partnerships: Chemoselective Ultrafast Addition to Imines and Quinolines Under Aerobic Ambient Temperature Conditions

Shattering the long-held dogma that organolithium chemistry needs to be performed under inert atmospheres in toxic organic solvents, chemoselective addition of organolithium reagents to non-activated imines and quinolines has been accomplished in green, b

Mechanistic insights into C-H amination via dicopper nitrenes

We examine important reactivity pathways relevant to stoichiometric and catalytic C-H amination via isolable β-diketiminato dicopper alkylnitrene intermediates {[Cl2NN]Cu}2(μ-NR). Kinetic studies involving the stoichiometric aminatio

Metal-free catalytic hydrogenation of enamines, imines, and conjugated phosphinoalkenylboranes

(Chemical Equation Presented) The metal-free hydrogen activator 1 catalyzes the unique P/B hydrogenation of the frustrated Lewis pair 3, which itself is inactive toward H2 under the applied conditions, to yield the hydrogenation product 4. System 1/2 (5 mol%) also catalyzes the hydrogenation of a bulky ketimine and of enamines under mild conditions (2.5 bar H2, RT) to yield the respective amines.

Regio- and stereoselective dirhodium(II)-catalysed intramolecular C-H insertion reactions of α-diazo-α-(dialkoxyphosphoryl)acetamides and -acetates

α-Diazo-α-(dialkoxyphosphoryl)acetates and -acetamides afforded α-(dialkoxyphosphoryl)lactones and lactams, respectively, in moderate to high yields through dirhodium(II)-catalysed intramolecular carbon-hydrogen insertion reactions. In the case of α-diazo

Transition Structure Geometries for Transfers of Neutral and Anionic Nitrogen to Lithiated Carbanions

The geometries of nucleophilic substitutions at neutral and anionic nitrogen by organolithium species have been investigated. The demonstration of an intramolecular conversion of 9 to 10 provides an endocyclic restriction test which supports a trigonal bipyramidal transition structure for nitrogen transfer. A lack of isotopic scrambling of 12a-18O during nitrogen transfer is taken to rule out reaction via an oriented ion pair. Attempted endocyclic restriction tests for transfers of formally anionic nitrogen with 32 and 33 were not successful. Reactions of n-butyl, s-butyl and tert-butyllithium reagents with 16, 23, 30, 31, and 36-38 generally afford higher yields with increasing substitution at the carbon of the organolithium reagent and with decreasing substitution adjacent to the nitrogen of the aminating reagent. These results are consistent with trigonal bipyramidal transition states for nucleophilic displacements of oxygen by carbon at neutral and anionic nitrogen.