58268-28-3

Upstream product

• 123-75-1 pyrrolidine 
• 451-40-1 phenyl benzyl ketone 
• 501-65-5 diphenyl acetylene 

Downstream Products

• 908094-04-2 phenyldiazomethane 
• 94191-34-1 [2,2-Diphenyl-1-pyrrolidin-1-yl-eth-(Z)-ylidene]-phosphoramidic acid diphenyl ester 
• 88875-34-7 [1-Phenyl-1-pyrrolidin-1-yl-meth-(Z)-ylidene]-phosphoramidic acid diphenyl ester 
• 101137-58-0 β-pyrrolidin-1-ylstilbene-α-thiocarbaldehyde 
• 103-30-0 (E)-1,2-diphenyl-ethene 
• 1939-16-8 1-bibenzyl-α-yl-pyrrolidine 

Relevant academic research and scientific papers

Highly efficient Rh(I)-catalyzed asymmetric hydrogenation of enamines using monodente spiro phosphonite ligands

A highly enantioselective hydrogenation of nonfunctionalized enamines has been developed by using rhodium complexes of chiral spiro phosphonite ligands, providing chiral tertiary amines in excellent enantioselectivities. Copyright

Alkali metal and stoichiometric effects in intermolecular hydroamination catalysed by lithium, sodium and potassium magnesiates

Main group bimetallic complexes, while being increasingly used in stoichiometric deprotonation and metal-halogen exchange reactions, have not yet made a significant impact in catalytic applications. This paper explores the ability of alkali metal magnesiates to catalyse the intermolecular hydroamination of alkynes and alkenes using sytrene and diphenylacetylene as principle setting model substrates. By systematically studying the role of the alkali-metal and the formulation of the heterobimetallic precatalyst, this study establishes higher order potassium magnesiate [(PMDETA)2K2Mg(CH2SiMe3)4] (7) as a highly effective system capable of catalysing hydroamination of styrene and diphenylacetylene with several amines while operating at room temperature. This high reactivity contrasts with the complete lack of catalytic ability of neutral Mg(CH2SiMe3)2, even when harsher reaction conditions are employed (24 h, 80 °C). A pronounced alkali metal effect is also uncovered proving that the alkali metal (Li, Na, or K) is not a mere spectating counterion. Through stoichiometric reactions, and structural and spectroscopic (DOSY NMR) investigations we shed some light on the potential reaction pathway as well as the constitution of key intermediates. This work suggests that the enhanced catalytic activity of 7 can be rationalised in terms of the superior nucleophilic power of the formally dianionic magnesiate {Mg(NR2)4}2- generated in situ during the hydroamination process, along with the ability of potassium to engage in π-interactions with the unsaturated organic substrate, enhancing its susceptibility towards a nucleophilic attack by the amide anion.

Which Factors Control the Nucleophilic Reactivities of Enamines?

Changes in rate constants, equivalent to changes in Gibbs energies of activation ΔG≠, are commonly referred to as kinetic effects and differentiated from thermodynamic effects (ΔrG°). Often, little attention is paid to the fact that structural effects on ΔG≠ are composed of a thermodynamic (ΔrG°) and a truly kinetic (intrinsic) component (ΔG0≠), as expressed by the Marcus equation. Rate and equilibrium constants have been determined for a number of reactions of enamines with benzhydrylium ions (Aryl2CH+), which has allowed the determination of Marcus intrinsic barriers and a differentiated analysis of structure–reactivity relationships. To our knowledge, this is the first report in which the Lewis basicity of a πCC bond towards carbon-centered Lewis acids (for example, carbenium ions) has quantitatively been determined. The synthesis, structures, and properties of deoxybenzoin-derived enamines ArCH=C(Ph)NR2, which have been designed as reference nucleophiles for the future quantification of electrophilic reactivities, are explicitly described.

Stereo- and regioselective gold-catalyzed hydroamination of internal alkynes with dialkylamines

We report the use of a P,N-ligand to support a gold complex as a state-of-the-art precatalyst for the stereoselective hydroamination of internal aryl alkynes with dialkylamines to afford E-enamine products. Substrates featuring a diverse range of functional groups on both the amine (ether, sulfide, N-Boc amine, fluoro, nitrile, nitro, alcohol, N-heterocycles, amide, ester, and carboxylic acid) and alkyne (ether, N-heterocycles, N-phthalimide amines, and silyl ethers) are accommodated with synthetically useful regioselectivity.

METHOD FOR THE PREPARATION OF DIARYLISOXAZOLE SULFONAMIDE COMPOUNDS AND INTERMEDIATES

The disclosure provides a method for the preparation of a diarylisoxazolé sulfonamide compound comprising contacting a deoxybenzoin with a secondary amine to form a diarylenamine compound; contacting the diarylenamine compound with an acetylating agent to form an acetyl diarylenamine compound; contacting the acetyl diarylenamine compound with a source of hydroxylamine to form an diaryl isoxazolol compound; eliminating water from the diaryl isoxazolol compound to form a diaryl isoxazole compound, chlorosulfonating the diarylisoxazole compound to form a chlorosulfonyl diaryl isoxazole compound; and contacting the chlorosulfonyl diaryl isoxazole compound with a source of ammonia to form the diarylisoxazole sulfonamide compound.

Formation and Decomposition of 1,2,3-Triazolines Prepared from Diphenyl Phosphorazidate (DPPA) and Enamines of Diaryl-Type Ketones

The pyrrolidine enamine 1 of deoxybenzoin reacted with diphenyl phosphorazidate (DPPA, (C6H5O)2P(O)N3) to give two amidines, the 1,2-migration product 7a and the 1,3-dipolar elimination product 8a in a ratio of 77:23.The reaction of DPPA with the enamine