Biomimetic asymmetric Michael addition reactions in water catalyzed by amino-containing β-cyclodextrin derivatives

Nineβ‐cyclodextrin derivatives containing an amino group were synthesized via nucleophilic sub‐stitution from mono（6‐O‐p‐tolylsulfonyl）‐β‐cyclodextrin and used in asymmetric biomimetic Mi‐chael addition reactions in water at room temperature. The mechanism responsible for the moder‐ate activity and enantioselectivity of the β‐cyclodextrin derivatives was explored using nuclear magnetic resonance spectroscopy, namely 2D 1H rotating‐frame overhauser effect spectroscopy （ROESY）, ultraviolet absorption spectroscopy, and quantum chemical calculations, which provide a useful technique for investigating the formation of inclusion complexes. The effects of the pH of the reaction medium, theβ‐cyclodextrin derivative dosage, the structure of the modifying amino group, and various substrates on the yield and enantioselectivity were investigated. The results indicated that these factors had an important effect on the enantiomeric excess （ee） in the reaction system. Experiments using a competitor for inclusion complex formation showed that a hydrophobic cavity is necessary for enantioselective Michael addition. A comparison of the reactions using 4‐nitro‐β‐nitrostyrene and 2‐nitro‐β‐nitrostyrene showed that steric hindrance improved the enan‐tioselectivity. This was verified by the optimized geometries obtained from quantum chemical cal‐culations. An ee of 71%was obtained in the asymmetric Michael addition of cyclohexanone and 2‐nitro‐β‐nitrostyrene, using （S）‐2‐aminomethylpyrrolidine‐modified β‐CD as the catalyst, in an aqueous buffer solution, i.e., CH3COONa‐HCl （pH 7.5）.

Michael Addition of Nitroalkanes to CF_3CCl_2COCH=CHPh: A Facile Route to Fluorine-containing γ-Nitro Ketones

Nitroalkanes react smoothly with CF_3CCl_2COCH=CHPh via Michael addition in the presence of inorganic bases such as KF/Al2O3 or K2CO3, giving fluorinecontaining γ-nitro ketones in good yields.

TDDFT Study on Different Sensing Mechanisms of Similar Cyanide Sensors Based on Michael Addition Reaction

The solvents and substituents of two similar fluorescent sensors for cyanide, 7-diethylamino- 3-formylcoumarin （sensor a） and 7-diethylamino-3-（2-nitrovinyl）coumarin （sensor b）, are proposed to account for their distinct sensing mechanisms and experimental phenomena. The time-dependent density functional theory has been applied to investigate the ground states and the first singlet excited electronic states of the sensor as well as their possible Michael reaction products with cyanide, with a view to monitoring their geometries and photophysieal properties. The theoretical study indicates that the protic water solvent could lead to final Michael addition product of sensor a in the ground state, while the aprotic acetonitrile solvent could lead to carbanion as the final product of sensor b. Furthermore, the Michael reaction product of sensor a has been proved to have a torsion structure in its first singlet excited state. Correspondingly, sensor b also has a torsion structure around the nitrovinyl moiety in its first singlet excited state, while not in its carbanion structure. This could explain the observed strong fluorescence for sensor a and the quenching fluorescence for the sensor b upon the addition of the cyanide anions in the relevant sensing mechanisms.

Guanidinium Lactate Ionic Liquid: An Efficient and Recycling Catalyst for Michael Addition Reaction

A facile and efficient 1, 4-conjungate addition（Michael addition） reaction of active methylene compounds to aft-unsaturated compounds, catalyzed by guanidinium lactate ionic liquid（IL9）, has been developed. A range of chalcones and nitroalkenes together with active methylene compounds have been converted smoothly to the corresponding products in high yields.

Modification of Nano-alumina Surface by Michael Addition Reaction

A general method for modification of nano-alumina surface is investigated using Michael addition reaction with α,β-unsaturated carbonyl compounds.

[Bmim]OAc Catalyzed Michael Addition of Active Methylene to α,β-Unsaturated Carboxylic Esters and Nitriles

Michael addition of active methylene compounds to α,β-unsaturated carboxylic esters and nitriles was effectively catalyzed by a basic ionic liquid, 1-butyl-3-methylimidazolium acetate（[Bmim]OAc）. The his-addition products were selectively obtained in high yields under mild reaction conditions.

MICHAEL ADDITION OF NITROALKANE TO α,β-UNSATURATED CARBONYL COMPOUNDS ON KF / Al_2O_3/ PEG4000

Michael addition of nitroalkanes to α,β-unsaturated carbonyl compounds occurs in the presence of KF/AI_2O_3/PEG4000 without solvent.Yields are fair to good and work-ups are easy.

Nitrosonium(NO^+) catalyzed Michael addition of indoles to unsaturated enones

An efficient Michael addition of indoles to unsaturated enones, such as chalcones and β-nitrostyrenes, was achieved in the presence of a catalytic amount of nitrosonium tetrafluoroborate in ethyl ether. 2007 Long Min Wu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Tetramethylguanidium Lactate Ionic Liquid: Catalyst-free Medium for Michael Addition Reaction

A catalyst-free, facile and efficient Michael addition reaction of active methylene compounds as well as nitromethane with chalcones catalyzed by guanidinium lactate ionic liquid was done. A series of chalcones, nitromethane, and active methylene compounds were converted smoothly to the corresponding products in high yields. The simple procedure, very mild conditions, high yields, and reuse of the IL without any loss of catalytic activity make this protocol considerably attractive for academic researches and practical applications.

Diastereoselective Michael Addition of (4'S)-Ethyl-3-(2',2'-Dimethyl-1',3'- dioxolan-4'-yl) acrylate with Furyl Lithium

Michael addition of the chiral alpha,beta -unsaturated ester 2 with furyl lithium proceeded in syn manner with excellent diastereoselectivity. The diastereoselectivity was not affected by the configuration of the double bond in 2.

Vicarious Michael Addition

C-H bond can undergo vicarious Michael addition reaction （VMA） with doubleactivated double bond in the absence of strong base and catalyst under mild conditions. Intramolecular H-bonding, electron-withdrawing inductive effect, and steric hindrance at aposition of nucleophile facilitates C-H addition over N-H addition. By using VMA, high branching multiplicity, novel branching pattern, controllable density and distribution of functional groups can be envisioned for novel dendrimer synthesis.

Michael Addition of Amines to Activated Alkenes Promoted by Zn/NH_4Cl System

A Zn/NH4Cl system was exploited at room temperature to promote the Michael addition reaction of various primary and secondary amines with α,β-unsaturated esters,nitriles,amides,and ketones to give the corresponding saturated amines under the mild condition in high yield.

Michael Additions of Activated Methylene Compounds to α,β-Unsaturated Esters Promoted by Samarium (Ⅲ) Iodide

Promoted by SmI3 β -diketones， β-ketoesters and α -cyano esters were added to α,β -unsaturated esters to form δ-carbonyl esters in mild conditions in moderate to good yields.

Organocatalyzed Highly Efficient Michael Addition of Malonate Derivatives to α,β-Unsaturated Ketones Using Chiral Schiff Bases

An efficient enantioselective Michael addition of ethyl-2-cyanoacetate and diethyl malonate to α,β-unsaturated ketones catalyzed by a simple chiral Schiff base, and products were obtained in good yields at room temperature.

Wood pulp industry by-product valorization for acrylate synthesis and bio-based polymer development via Michael addition reaction

It is crucial to adapt the processing of forest bio-resources into biochemicals and bio-based ad-vanced materials in order to transform the current economic climate into a greener economy.Tall oil,as a by-product of the Kraft process of wood pulp manufacture,is a promising resource for the extraction of various value-added products.Tall oil fatty acids-based multifunctional Michael acceptor acrylates were developed.The suitability of developed acrylates for polymerization with tall oil fatty acids-based Michael donor acetoacetates to form a highly cross-linked polymer ma-terial via the Michael addition was investigated.With this novel strategy,valuable chemicals and innovative polymer materials can be produced from tall oil in an entirely new way,making a significant contribution to the development of a forest-based bioeconomy.Two different tall oil-based acrylates were successfully synthesized and characterized.Synthesized acrylates were successfully used in the synthesis of bio-based thermoset polymers.Obtained polymers had a wide variety of mechanical and thermal properties(glass transition temperature from-12.1 to 29.6°C by dynamic mechanical analysis,Young’s modulus from 15 to 1760 MPa,and stress at break from 0.9 to 16.1 MPa).Gel permeation chromatography,Fourier-transform infrared(FT-IR)spectroscopy,matrix-assisted laser desorption/ionization-time of flight mass spectrometry,and nuclear magnetic resonance were used to analyse the chemical structure of synthesized acrylates.In addition,various titration methods and rheology tests were applied to characterize acrylates.The chemical composition and thermal and mechanical properties of the developed polymers were studied by using FT-IR,solid-state nuclear magnetic resonance,thermal gravimetric analy-sis,differential scanning calorimetry,dynamic mechanical analysis,and universal strength testing apparatus.

Solvent-free Michael addition reaction of fluorene with chalcon

A series of novel Michael addition products of fluorene to chalcone were obtained in the presence of sodium hydroxide under solvent-free condition. The advantages of this procedure were mild reaction conditions, simple protocol, and high yields. The structures of the products were characterized by IR, 1H NMR, MS and X-ray diffraction. The crystal of the new compound 3 h is Triclinic, space group P-1 with a = 0.97352（6） nm, b = 1.08918（7） nm, c = 2.58418（16） nm, α = 80.1400（10）°, β = 79.5490（10）°, γ = 64.2440（10）°, V = 2.4137（3） nm3, Z = 4, Dc=1.220 g/cm3,μ = 0.286 mm-1, F（000） = 920, R = 0.0656 and wR = 0.1554 for 5664 observed reflection with I 〉 2σ（I）.

A novel solid state Michael addition reaction of N-heterocyclic compounds containing active C-H bond

In this paper, a novel solid state Michael-type addition reaction of N-heterocyclic compounds containing the active-CH group was investigated. 3-Methyl-1-phenyl-5-pyrazolone (MPP) and indole (In) reacted with 4-arylmethylene-3-methyl-1-phenyl-5-pyrazolone (1) in the solid state at room temperature to give the corresponding adducts, aryl-4,4'-bis(5-hydroxy-3-methyl-1-phenyl-pyrazolyl) methane (2a-n) and 1-aryl-1-(5'-hydroxy-3'-methyl-1'-phenyl-4'-pyrazolyl)-1-(3 ''-indolyl) methane (3a-n), respectively. This is a feasible method for preparing the compound which contains two heterocyclic groups on the same carbon.

Iron catalyzed Michael addition: Chloroferrate ionic liquids as efficient catalysts under microwave conditions

The iron containing ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate （[C4mim]C1/FeCl3; Z = 0.5） proved to be an efficient catalyst for the solvent-free metal catalyzed Michael addition of β-keto esters and enones. Due to the ionic structure of the catalyst, a significant acceleration of the reaction rate was observed under microwave conditions. Furthermore, recycling of the ionic liquid catalyst could be performed after simply distilling off the products.

A Green and Highly Efficient Protocol for Catalyst-free Kno- evenagel Condensation and Michael Addition of Aromatic Al- dehydes with 1,3-Cyclic Diketones in PEG-400

A convenient, highly efficient and green approach for synthesis of tetraketones from aromatic aldehydes with dimedone and 1,3-indanedione at room temperature in PEG-400 is described. The use of PEG-400 as the reaction medium and avoiding the use of any catalyst makes the process environmentally benign. Seven new compounds are reported.