60547-34-4

Upstream product

• 1121-66-0 2-Cyclohepten-1-one 
• 917-54-4 methyllithium 
• 1184-53-8 methylcopper 
• 142950-82-1 (R)-(-)-1-(2-amino-2-phenylethyl)piperidine 
• 186581-53-3 diazomethane 
• 67-56-1 methanol 
• 60-29-7 diethyl ether 
• 13368-65-5 (3R)-3-methylcyclohexanone 
• 557-20-0 diethylzinc 
• 544-97-8 dimethyl zinc(II) 
• 129380-08-1 (S)-N-methyl-1-phenyl-2-(piperidin-1-yl)ethanamine 
• 148054-62-0 (S)-N-methyl-1-phenyl-2-(4-methyl-1-piperidinyl)ethanamine 
• 75-16-1 methylmagnesium bromide 
• 75-24-1 trimethylaluminum 

Relevant academic research and scientific papers

Asymmetric conjugate addition of organocopperamidophosphine reagents to cycloalkenones

Mediated by a noncovalently bound chiral amidophosphine ligand 1, reaction of organocoppers with cycloalkenones 2 afforded the corresponding 3-substituted cycloalkanones 3 in 95-68% ee.

Inversions in asymmetric conjugate addition reaction of cyclic enones catalyzed by the Cu/NHC-AgX system: Factors affecting the stereoselective formation of both enantiomers

A switchable enantioselectivity was achieved in a Cu-catalyzed asymmetric conjugate addition (ACA) reaction. The ethylene-bridged, hydroxyamide-functionalized NHC-AgI complex, readily accessible from a chiral β-amino alcohol, was found to be a versatile c

Enantioselectivity switch in copper-catalyzed conjugate addition reactions under the influence of a chiral N-heterocyclic carbene-silver complex

The asymmetric 1,4-addition of Et2Zn to 2-cyclohexen-1-one using a Cu(i) salt/N-heterocyclic carbene (NHC)-Ag complex catalytic system afforded optically active 3-ethylcyclohexanone. The reversal of enantioselectivity using the same catalytic s

Cp2ZrMeCl: A Reagent for Asymmetric Methyl Addition

The use of Cp2ZrMeCl is described as a source of nucleophilic methyl in asymmetric catalysis. This easily prepared reagent is bench stable, weighable in air, and generally useful in highly enantioselective copper-catalyzed addition reactions at room temperature. Methyl is successfully (generally >90% ee) added in 1,4-additions to cyclic and acyclic α,β-unsaturated ketones to provide tertiary and quaternary centers. Examples of catalyst controlled diastereoselective 1,6-addition and dynamic kinetic asymmetric allylic alkylation reactions are also reported. The reagent is used in the catalytic asymmetric synthesis of naturally occurring fragrance (R)-(-)-muscone (82% yield, 91% ee).

Preparation and characterization of new C2- and C 1-symmetric nitrogen, oxygen, phosphorous, and sulfur derivatives and analogs of TADDOL. part i

The chloro alcohols 4-6 derived from TADDOLs (=α,α, α′,α′-tetraaryl-1,3-dioxolan-4,5-dimethanols) are used to prepare corresponding sulfanyl alcohols, ethers, and amines (Scheme 1 and Table 1). The dithiol analog of TADDOL and derivatives thereof, 45-49,

Hydroxy-amide functionalized azolium salts for Cu-catalyzed asymmetric conjugate addition: Stereocontrol based on ligand structure and copper precatalyst

A series of hydroxy-amide functionalized azolium salts have been designed and synthesized for Cu-catalyzed asymmetric conjugate addition reaction. The (CH2)2-bridged hydroxy-amide functionalized azolium ligand precursors 2, in addition to the previously reported CH2-bridged azolium salts 1, have been prepared from readily available enantiopure β-amino alcohols. The combination of a Cu species with 1 or 2 efficiently promoted the 1,4-addition reaction of cyclic enones with dialkylzincs. For example, the reaction of 2-cyclohepten-1-one (17) with Bu2Zn in the presence of catalytic amounts of Cu(OTf)2 and 1 gave (S)-3-butylcycloheptanone (20) in 99% yield and 96% ee. On the other hand, when the reaction was carried out under the influence of Cu(OTf)2 combined with 2, (R)-20 in preference to (S)-20 was obtained in 98% yield and 80% ee. In this manner, the enantioselecvity was switched by controlling the structure of chiral ligand. Additionally, the reversal of enantioselectivity was also achieved by changing the Cu precatalyst from Cu(OTf)2 to Cu(acac)2 with the same ligand. The combination of Cu(acac) 2 with CH2-bridged azolium salt 1 in the reaction of 17 with Bu2Zn led to formation of (R)-20 as a major product in 55% yield and 80% ee. This result was in contrast to the Cu(OTf)2/1 catalytic system, where the 1,4-adduct with opposite configuration was obtained. Moreover, use of the Cu(acac)2/2 catalytic system produced (S)-20, while (R)-20 was formed by the Cu(OTf)2/2 catalytic system. Thus, it was found that either varying the linker of the chiral ligands or changing the counterion of Cu species between a OTf and acac ligand initially on the metal led to dual enantioselective control in the 1,4-addition reaction.

Enantioselective copper-catalyzed 1,4-addition of dialkylzincs to enones using a novel N,N,P-Cu(II) complex

Enantioselective copper-catalyzed 1,4-additions of dialkylzincs to enones were carried out in the presence of 1 mol % of Cu(OTf)2 and 2.5 mol % of an N,N,P-ligand possessing a tert-butyl group at the adjacent position of the nitrogen of pyridin

Enantioselective copper-catalyzed 1,4-addition of dialkylzincs to enones followed by trapping with allyl iodide derivatives

Enantioselective copper-catalyzed 1,4-addition of dialkylzincs to enones proceeded in the presence of 0.1 mol% of Cu(OTf)2 and 0.25 mol% of an N,N,P-ligand containing a quinoline moiety to afford the corresponding conjugated adducts in 99%ee. The intermediate zinc enolates were trapped with substituted allyl iodides to give disubstituted ketones with high diastereoselectivity and enantioselectivity.

Copper-catalyzed asymmetric 1,4-conjugate addition of dialkylzinc to enones

Asymmetric 1,4-conjugation addition of dialkylzinc (diethylzinc and dimethylzinc) to cyclic enones, chalcone and nitroalkenes was achieved by a 25 mol% (R)-6,6'-Br2-BINOL(1f), 25 mol% CuSPh and 100 mol% dicyclohexylmethylamin(Cy2NMe) catalyst system. The Cu(I) catalyst system enables the cyclic enone, chalcone and nitroalkene generality with high enantioselectivity (up to84%ee) and isolated yield (up to 94%) under mild reaction conditions.

Thieme chemistry journal awardees - Where are they now? Asymmetric br?nsted acid catalyzed transfer hydrogenations

Asymmetric hydrogenations are of great importance in the synthesis of optically active amines. This account highlights the development of the first metal-free transfer hydrogenation that is both highly enantioselective and inspired by natures dehydrogen?ase. Further focus is given to the extension of this bioinspired process to provide a variety of valuable, biologically active products and natural products under mild reaction conditions. Georg Thieme Verlag Stuttgart - New York.