Green, efficient and practical Michael addition of arylamines to α,β-unsaturated ketones

The aza-Michael addition of aromatic amines to α,β-unsaturated ketones was carried out effectively at room temperature in good to excellent yields without any catalyst or solvent. It was significant that part of adducts could be collected in almost quantitative yield without column chromatography. This procedure offered a green, efficient, and practical approach for the synthesis of β-amino ketones.     

Highly effective and regioselective Michael addition of indoles to α,β-unsaturated ketones promoted by pentafluorophenylammonium triflate

A simple, inexpensive, environmentally friendly and efficient route for Michael addition of indoles to α,β-unsaturated ketones using pentafluorophenylammonium triflate (PFPAT) as a catalyst is described. Various indole derivatives were synthesized in good to excellent yields. The preparation of PFPAT catalyst from simple and readily available starting materials makes this method more affordable.     

Catalytic enantioselective conjugate addition of indoles to simple α,β-unsaturated ketones

Chiral [Al(salen)Cl] complex (10 mol%) in the presence of 2,6-lutidine (10 mol%) was found to be effective in catalysing the enantioselective Friedel-Crafts-type conjugate addition of indoles (3) to (E)-arylcrotyl ketones (2), furnishing the corresponding β-indolyl ketones in excellent yield and high enantioselectivity (ee up to 89%).     

Recyclable graphite oxide catalyzed Friedel-Crafts addition of indoles to α,β-unsaturated ketones

The Friedel-Crafts addition of indoles to α,β-unsaturated ketones, and nitro styrenes was studied with graphite oxide as catalyst. Various indole derivatives were synthesized in good to excellent yields. The preparation of graphite oxide catalyst from simple and readily available starting materials makes this method more affordable. The heterogeneous graphite oxide can be easily recovered and recycled up to five cycles without loss of activity.     

A highly efficient michael addition of indoles to α,β-unsaturated electron-deficient compounds in acidic SDS micellar media

The Michael addition of indoles to α,β-unsaturated electron deficient compounds was catalyzed efficiently at room temperature in acidic micellar solution of sodium dodecyl sulfate (SDS). The substitution on the indole nucleus occurred exclusively at the 3-position in good to excellent yields, and no N-alkylation products were observed.     

Phospha-Michael addition of phosphorus nucleophiles to α,β-unsaturated malonates using 3-aminopropylated silica gel as an efficient and recyclable catalyst

3-Aminopropylated silica gel, which is prepared from commercially available and cheap starting materials, is introduced as an efficient and recyclable catalyst for the phospha-Michael addition of phosphorus nucleophiles to α,β-unsaturated malonates. Short reaction times, mild reaction conditions, ease of recovery and catalyst reusability make this method a new, economic and waste-free chemical process for the synthesis of β-phosphonomalonates.     

Organocatalytic and direct asymmetric vinylogous Michael addition of 3-cyano-4-methylcoumarins to α,β-unsaturated ketones

The first highly regio-, chemo-, and enantio-selective direct vinylogous Michael addition of 3-cyano-4-methylcoumarin derivatives to α,β-unsaturated ketones is described, employing readily available 9-amino-9-deoxy-epiquinine as the iminium organocatalyst.     

Cobalt-catalyzed conjugate addition of silylacetylenes to α,β-unsaturated ketones

Catalytic addition of silylacetylenes to α,β-unsaturated ketones proceeded in the presence of a cobalt complex coordinated with a bisphosphine ligand to give high yields of β-alkynylketones.     

Acidic-functionalized ionic liquid as an efficient, green and reusable catalyst for hetero-Michael addition of nitrogen, sulfur and oxygen nucleophiles to α,β-unsaturated ketones

A series of acidic-functionalized ionic liquids were synthesized and applied to the hetero-Michael addition of nitrogen, sulfur and oxygen nucleophiles to α,β-unsaturated ketones under solvent-free conditions. Notably, 1-methylimidazolium p-toluenesulfonic ([Hmim]OTs) was found to be the most efficient catalyst and could realize "homogeneous catalysis, two-phase separation". Additionally, the catalytic system has wide substrate scope and good to excellent yields (up to 99%) could be obtained at room temperature.     

Asymmetric conjugate addition of malonate to α,β-unsaturated ketones in water using a perfluoroalkanesulfonamide organocatalyst

Perfluoroalkanesulfonamide organocatalyst 7 efficiently promotes asymmetric Michael additions of malonates to enones in cyclohexane or water to produce the corresponding addition products with excellent yields and with up to 99% ee.     

Asymmetric Michael addition of substituted rhodanines to α,β-unsaturated ketones catalyzed by bulky primary amines

A bulky group was introduced by design into a diamine catalyst, and a series of robust and tunable bulky chiral primary amine catalysts were developed and successfully applied in the direct conjugate addition of substituted rhodanines to α,β-unsaturated ketones. High yields (up to 99%) and excellent diastereoselectivities (up to 99:1 dr) and enantioselectivities (up to 98% ee) were observed.     

Water-compatible iminium activation: highly enantioselective organocatalytic Michael addition of malonates to α,β-unsaturated enones

The highly enantioselective Michael addition of malonates to α,β-unsaturated ketones in water was reported to be catalyzed by a primary-secondary diamine catalyst containing a long alkyl chain. This asymmetric Michael addition process was found to be effective for a variety of α,β-unsaturated ketones.     

Intermediate as catalyst: catalytic asymmetric conjugate addition of nitroalkanes to α,β-unsaturated thioamides

Catalytic asymmetric conjugate addition of nitroalkanes to α,β-unsaturated thioamides is promoted by a mesitylcopper/(R)-DTBM-Segphos precatalyst, affording γ-nitrothioamides in moderate to high syn-selectivity and excellent enantioselectivity. The intermediate Cu-thioamide enolate functions as a soft Lewis acid/hard Br?nsted base cooperative catalyst to drive the catalytic cycle efficiently under proton transfer conditions.     

Enantioselective organocatalytic conjugate addition of α-nitroacetate to α,β-unsaturated ketones in water

The catalytic enantioselective conjugate addition reaction of α-nitroacetate to α,β-unsaturated ketones promoted by chiral bifunctional organocatalysts is described. The treatment of α-nitroacetate to α,β-unsaturated ketones under aqueous-phase reaction conditions afforded the corresponding Michael adducts with high enantioselectivity. The conjugate addition adducts are easily converted to chiral δ-keto nitroalkanes and δ-keto esters.     

Conjugate addition to α,β-unsaturated ketones with mixed lithium triorganozincates

Lithium Triorganozincates of the type RR′₂ZnLi, where R′ = Me and R = n-Bu or sec-Bu, efficiently transfer the R group in a 1,4 fashion to α,β-unsaturated ketones.     

Ytterbium triflate hydrate catalyzed Michael addition and cyclocondensation of α,β-unsaturated ketones with active methylene compounds

Catalyzed by ytterbium（III） triflate hydrate [Yb（OTf）3.xH20], the Michael addition and cyclocondensation of α,β-unsaturated ketones with active methylene compounds to afford the 1,4-adducts and benzo[b]pyran derivatives, respectively were studied.     

Michael addition of nitroalkanes to nonactivated α,β-unsaturated δ-thiolactams: reactivity, diastereoselectivity, and comparison to α,β-unsaturated δ-lactams

Aliphatic nitrocompounds add to nonactivated α,β-unsaturated δ-thiolactams leading to 4-nitroalkyl functionalized δ-thiolactams in good yields. The addition is a stereocontrolled process with respect to substituents at C-6, and takes place producing trans 4,6-disubstituted adducts in most cases. Ease of the addition has been studied in relation to the structure of the δ-thiolactam acceptors, within the FMO-theory. Comparative study with analogous δ-lactams has shown the advantages of α,β-unsaturated δ-thiolactams in Michael addition and indicated high prospects of these compounds in the synthesis of 4-functionalized piperidine derivatives.     

Enantioselective sulfa-Michael addition of thioacids to α,β-unsaturated ketones with bifunctional organocatalyst

Organocatalytic conjugate addition of thioacids to α,β-unsaturated ketones has been studied in the presence of cinchona alkaloid derived urea catalyst. Both the enantiomers of products are accessible with the same level of enantioselectivity using pseudoenantiomeric quinine/quinidine derived catalysts. The catalytic process provides optically active thioesters with high chemical yields (up to 99%) and useful enantioselectivity (up to 83% ee). The reaction was performed with 1 mol % of catalyst in toluene at room temperature. A transition state model has been proposed to explain the stereochemical outcome of the reaction.