2. Essential Components: Earlier Developments 5449 2.1. Activated alkenes/alkynes 5450 2.1.1. Acyclic activated alkenes/ alkynes 5450 2.1.2. Cyclic activated alkenes 5451 2.2. Electrophiles 5451 2.3. Catalysts 5452 3. Essential Components: Recent Developments 5452 3.1. Activated Alkenes/Alkynes 5452 3.2. Electrophiles 5460 3.3. Catalysts 5477 4. Asymmetric Baylis-Hillman Reaction: Earlier Developments 5495

Recent contributions from the Baylis-Hillman reaction to organic chemistry.

Asymmetric aldol reactions are a powerful method for the construction of carbon–carbon bonds in an enantioselective fashion. Historically this reaction has been performed in a stoichiometric fashion to control the various aspects of chemo-, diastereo-, regio- and enantioselectivity, however, a more atom economical approach would unite high selectivity with the use of only a catalytic amount of a chiral promoter. This critical review documents the development of direct catalytic asymmetric aldol methodologies, including organocatalytic and metal-based strategies. New methods have improved the reactivity, selectivity and substrate scope of the direct aldol reaction and enabled the synthesis of complex molecular targets (357 references).

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The Direct Catalytic Asymmetric Aldol Reaction

Ionic liquids are solvents that consist entirely of ions. These nonvolatile and nonflammable solvents offer interesting opportunities for lanthanide and actinide chemistry. They can replace the organic phase in solvent extraction systems and can be used as nonaqueous electrolytes for electrodeposition of metals. Ionic liquids could find applications in the nuclear fuel cycle. Lanthanide coordination compounds or lanthanide-containing nanoparticles can be obtained via ionothermal or microwave-assisted synthesis in ionic liquids. Lanthanide-doped ionogels are a new type of luminescent hybrid materials. Ionic liquids can serve as solvents for lanthanide-mediated organic reactions, and there are several examples of high reactivity and selectivity.

Lanthanides and Actinides in Ionic Liquids

In recent years, the designer nature of ionic liquids (ILs) has driven their exploration and exploitation in countless fields among the physical and chemical sciences. A fair measure of the tremendous attention placed on these fluids has been attributed to their inherent designer nature. And yet, there are relatively few examples of reviews that emphasize this vital aspect in an exhaustive or meaningful way. In this critical review, we systematically survey the physicochemical properties of the collective library of ether- and alcohol-functionalized ILs, highlighting the impact of ionic structure on features such as viscosity, phase behavior/transitions, density, thermostability, electrochemical properties, and polarity (e.g. hydrophilicity, hydrogen bonding capability). In the latter portions of this review, we emphasize the attractive applications of these functionalized ILs across a range of disciplines, including their use as electrolytes or functional fluids for electrochemistry, extractions, biphasic systems, gas separations, carbon capture, carbohydrate dissolution (particularly, the (ligno)celluloses), polymer chemistry, antimicrobial and antielectrostatic agents, organic synthesis, biomolecular stabilization and activation, and nanoscience. Finally, this review discusses anion-functionalized ILs, including sulfur- and oxygen-functionalized analogs, as well as choline-based deep eutectic solvents (DESs), an emerging class of fluids which can be sensibly categorized as semi-molecular cousins to the IL. Finally, the toxicity and biodegradability of ether- and alcohol-functionalized ILs are discussed and cautiously evaluated in light of recent reports. By carefully summarizing literature examples on the properties and applications of oxy-functional designer ILs up till now, it is our intent that this review offers a barometer for gauging future advances in the field as well as a trigger to spur further contemplation of these seemingly inexhaustible and—relative to their potential—virtually untouched fluids. It is abundantly clear that these remarkable fluidic materials are here to stay, just as certain design rules are slowly beginning to emerge. However, in fairness, serendipity also still plays an undeniable role, highlighting the need for both expanded in silico studies and a beacon to attract bright, young researchers to the field (406 references).

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Ether- and Alcohol-Functionalized Task-Specific Ionic Liquids: Attractive Properties and Applications

2.3.3. Fluorinated Imines 7 2.3.4. Arylimino Acetates 8 2.3.5. In Situ Generated Iminium Ions 8 2.4. -Substituted Michael Acceptors 8 2.5. Formation of Unexpected Products 10 2.5.1. Reaction with Cyclic Enones 11 2.5.2. Reaction with Vinyl Ketones 11 2.5.3. Reaction with Acrolein 12 2.5.4. Reaction with Activated Allenes and Alkynes 12 2.5.5. Reaction of Salicyl N-Tosylimines 12 3. Stereoselective Synthesis 13 3.1. Use of Chiral Aldehydes 13 3.2. Use of Chiral Bases 13 3.3. Use of Chiral Phosphines 16 3.4. Use of a Chiral Sulfide 18 3.5. Use of an Organocatalyst Derived from BINOL 18 3.6. Use of a Chiral Ligand Derived from Thiourea 18 3.7. Use of Chiral Ionic Liquids 18 4. Alternative Access Pathways to -Aminocarbonyl Compounds 18

aza-Baylis−Hillman Reaction

Dy(OTf)3 in ionic liquid: an efficient catalytic system for reactions of indole with aldehydes/ketones or imines

Facile evolution of asymmetric organocatalysts in water assisted by surfactant brønsted acids

Hydroxyl ionic liquid (HIL)-immobilized quinuclidine for Baylis–Hillman catalysis: synergistic effect of ionic liquids as organocatalyst supports

Dy(OTf)3 immobilized in ionic liquids was found to be an efficient catalytic system for the reactions of indole with aldehydes/ketones or imines. Enhanced activity was observed. The use of ionic liquids as the reaction media allows facile separation and recycling of the catalyst.

Dy(OTf)3 in Ionic Liquid: An Efficient Catalytic System for Reactions of Indole with Aldehydes/Ketones or Imines.

Hydroxyl ionic liquid (HIL) has been explored as a novel support for Baylis–Hillman catalyst. The HIL-supported catalyst showed a better catalytic activity compared to other IL-immobilized catalyst that has no hydroxyl group attached to the IL scaffold. The hydroxyl group linked on IL played an important role in facilitating efficient catalysis under solvent-free conditions. The corresponding Baylis–Hillman and aza-Baylis–Hillman adducts were obtained in good to excellent yields in all cases examined. The HIL-supported quinuclidine can be readily recovered and reused for six times without significant loss of catalytic activity.

Xueling Mi

Papers

Dy(OTf)3 in ionic liquid: an efficient catalytic system for reactions of indole with aldehydes/ketones or imines

Facile evolution of asymmetric organocatalysts in water assisted by surfactant brønsted acids

Hydroxyl ionic liquid (HIL)-immobilized quinuclidine for Baylis–Hillman catalysis: synergistic effect of ionic liquids as organocatalyst supports

Dy(OTf)3 in Ionic Liquid: An Efficient Catalytic System for Reactions of Indole with Aldehydes/Ketones or Imines.

Hydroxyl Ionic Liquid (HIL)‐Immobilized Quinuclidine for Baylis—Hillman Catalysis: Synergistic Effect of Ionic Liquids as Organocatalyst Supports.