Osmium Catalyst for the Borrowing Hydrogen Methodology: α-Alkylation of Arylacetonitriles and Methyl Ketones

Complex [Os(η6-p-cymene)(OH)(IPr)]OTf is an efficient catalyst precursor for the α-alkylation of arylacetonitriles and methyl ketones with alcohols, which works with turnover frequencies between 675 and 176 h–1 for nitriles and between 194 and 28 h–1 for ketones.

Copper-Catalyzed Asymmetric Alkylation of β-Keto Esters with Xanthydrols

The copper(II) triflate-tert-butyl-bisoxazoline [Cu(OTf)2-t-Bu-BOX]-catalyzed asymmetric alkylation of β-keto esters using free benzylic alcohols such as xanthydrols, as alkylating agents, is herein described for the first time. This green protocol renders in general the corresponding products with good results in terms of both yields and enantioselectivities using different keto esters, even when quaternary stereocenters were created. The scope, limitations and mechanistic aspects of the process are also discussed.

Isobutane Alkylation Process Synthesis by means of Hybrid Simulation-Multiobjective Optimization

Multiobjective Generalized Disjunctive Programming (MO-GDP) optimization has been used for the synthesis of an important industrial process, isobutane alkylation. The two objective functions to be simultaneously optimized are the environmental impact, determined by means of LCA (Life Cycle Assessment), and the economic potential of the process. The main reason for including the minimization of the environmental impact in the optimization process is the widespread environmental concern by the general public. For the resolution of the problem we employed a hybrid simulation- optimization methodology, i.e., the superstructure of the process was developed directly in a chemical process simulator connected to a state of the art optimizer. The model was formulated as a GDP and solved using a logic algorithm that avoids the reformulation as MINLP -Mixed Integer Non Linear Programming-. Our research gave us Pareto curves compounded by three different configurations where the LCA has been assessed by two different parameters: global warming potential and ecoindicator-99.

Bis(2-aminobenzoimidazole)-Organocatalyzed Asymmetric Alkylation of Activated Methylene Compounds with Benzylic and Allylic Alcohols

The first organocatalyzed asymmetric alkylation of activated methylene compounds using benzylic and allylic alcohols as alkylating agents through dual hydrogen bond activation in an SN1-type reaction is reported. This green protocol employs a bis(2-aminobenzoimidazole) in combination with an achiral Brønsted acid as a bifunctional catalytic system and gives the alkylation products with moderate to good enantioselectivities. Although the scope of the reaction is limited, this methodology can be considered as complementary to existing metal-catalyzed processes. In addition, modest results were obtained in a first attempt to perform a metal-free asymmetric Tsuji–Trost reaction using allylic alcohols. Finally, the recovery and reusability of the organocatalyst is also achieved.

Insights into the Active Species of Nanoparticle-Functionalized Hierarchical Zeolites in Alkylation Reactions

Supported iron oxide nanoparticles have been incorporated onto hierarchical zeolites by microwave-assisted impregnation and mechanochemical grinding. Nanoparticle-functionalised porous zeolites were characterised by a number of analytical techniques such as XRD, N2 physisorption, TEM, and surface acidity measurements. The catalytic activities of the synthesised nanomaterials were investigated in an alkylation reaction. The results pointed to different species with varying acidity and accessibility in the materials, which provided essentially different catalytic activities in the alkylation of toluene with benzyl chloride under microwave irradiation, selected as the test reaction.

Organic reactions in ionic liquids:A new method for the synthesis of alkyl aryl sulfones by alkylation of sodium arenesulfinates with unactivated alkyl chlorides

A new method is reported for the synthesis of alkyl aryl sulfones by alkylation of sodium arenesulfinates with unactivated alkyl chlorides using ionic liquid based on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF 4) mixed with water (2:1) as reaction media. The ionic liquid can be reused and the procedure gives the sulfones in moderate yields.

Organic reactions in ionic liquids: an efficient method for the N-alkylation of benzotriazole

The N-alkylation of benzotriazole with alkyl halides proceeds efficiently in the presence of potassium hydroxide in ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]).

Organic reactions in ionic liquids:An efficient method for selective S-alkylation of 2-mercaptobenzothia(xa)zole with alkyl halides

Ionic liquids based on 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF6) and 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) are used as reusable reaction medium in the selective S-alkylation of 2-mercaptobenzothia(xa)zole with alkyl halides in the presence of potassium carbonate. This procedure is convenient, efficient, and generally gives rise to the S-alkylated product exclusively.

Organic reactions in ionic liquids: N-alkylation of cyclic imides with alkyl halides promoted by potassium fluoride

An ionic liquid based on 1-butyl-3-methylimidazolium hexafluorophosphate is used as an efficient reusable reaction medium in the N-alkylation of cyclic imides with alkyl halides promoted by fluoride ion.

Organic reactions in ionic liquids: N-alkylation of phthalimide and several nitrogen heterocycles

N-Alkylation of heterocyclic compounds bearing an acidic hydrogen atom attached to nitrogen with alkyl halides is accomplished in ionic liquids ([bmim]BF4 = 1-butyl-3-methylimidazolium tetrafluoroborate, [bmim]PF6 = 1-butyl-3-methylimida-zolium hexafluorophosphate, [buPy]BF4 = butylpyridinium tetra­fluoroborate) in the presence of potassium hydroxide as a base. In this manner, phthalimide, indole, benzimidazole, succinimide can be successfully alkylated. The procedure is convenient, efficient, and generally affords the N-alkylated product exclusively.

Organic reactions in ionic liquids:Alkylation of Meldrum's acid

The room temperature ionic liquid N-butylpyridinium tetrafluoroborate, [bpy]BF4 is used as a "green" recyclable alternative to classical molecular solvents for the alkylation of Meldrum's acid.

On the reactivity of naphthalene and biphenyl dianions: tying up loose ends concerning an SN2-ET dichotomy in alkylation reactions

Naphthalene and biphenyl dianions are interesting compounds that can be obtained by double reduction of the corresponding arenes in solution with certain alkali metals. These dianions are highly reactive and rather elusive species with very high laying and highly delocalized electrons. They share many aspects of the reactivity of the alkali metal they originated from and consequently behave primarily as strong electron transfer (ET) reagents. We report here kinetic evidence for a different type of reactivity in their alkylation reactions with alkyl fluorides. By using cyclopropylmethyl fluoride (c-C3H5CH2F) as a very fast radical probe, we were able to settle that this alkylation does not involve the classical electron transfer reaction followed by radical coupling between diffusing radicals, but supports the alternative SN2 concerted mechanism, discerning thus this mechanistic SN2-ET dichotomy.

The spermostatic and microbicidal actions of quinones and malemides : towards a dual-purpose contraceptive agent

There is an urgent need to develop safe, effective, dual-purpose contraceptive agents that combine the prevention of pregnancy with protection against sexually transmitted diseases. Here we report the identification of a group of compounds that on contact with human spermatozoa induce a state of “spermostasis,” characterized by the extremely rapid inhibition of sperm movement without compromising cell viability. These spermostatic agents were more active and significantly less toxic than the reagent in current clinical use, nonoxynol 9, giving therapeutic indices (ratio of spermostatic to cytotoxic activity) that were orders of magnitude greater than this traditional spermicide. Although certain compounds could trigger reactive oxygen species generation by spermatozoa, this activity was not correlated with spermostasis. Rather, the latter was associated with alkylation of two major sperm tail proteins that were identified as A Kinase-Anchoring Proteins (AKAP3 and AKAP4) by mass spectrometry. As a consequence of disrupted AKAP function, the abilities of cAMP to drive protein kinase A-dependent activities in the sperm tail, such as the activation of SRC and the consequent stimulation of tyrosine phosphorylation, were suppressed. Furthermore, analysis of microbicidal activity using Chlamydia muridarum revealed powerful inhibitory effects at the same low micromolar doses that suppressed sperm movement. In this case, the microbicidal action was associated with alkylation of Major Outer Membrane Protein (MOMP), a major chlamydial membrane protein. Taken together, these results have identified for the first time a novel set of cellular targets and chemical principles capable of providing simultaneous defense against both fertility and the spread of sexually transmitted disease.