Alkyl Halides In Water Research Articles

Fully Aqueous and Air-Compatible Cross-Coupling of Primary Alkyl Halides with Aryl Boronic Species: A Possible and Facile Method.

Aqueous transformations confer many advantages, including decreased environmental impact and increased opportunity for biomolecule modulation. Although several studies have been conducted to enable the cross-coupling of aryl halides in aqueous conditions, until now a process for the cross-coupling of primary alkyl halides in aqueous conditions was missing from the catalytic toolbox and considered impossible. Alkyl halide coupling in water suffers from severe problems. The reasons for this include the strong propensity for β-hydride elimination, the need for highly air- and water-sensitive catalysts and reagents, and the intolerance of many hydrophilic groups to cross-coupling conditions. Here, we report a broadly applicable and readily accessible process for the cross-coupling of water-soluble alkyl halides in water and air by using simple and commercially available bench-stable reagents. The trisulfonated aryl phosphine TXPTS in combination with a water-soluble palladium salt Na2PdCl4 allowed for the Suzuki-Miyaura coupling of water-soluble alkyl halides with aryl boronic acids, boronic esters, and borofluorate salts in mild, fully aqueous conditions. Multiple challenging functionalities, including unprotected amino acids, an unnatural halogenated amino acid within a peptide, and herbicides can be diversified in water. Structurally complex natural products were used as testbeds to showcase the late-stage tagging methodology of marine natural products to enable liquid chromatography-mass spectrometry (LC-MS) detection. This enabling methodology therefore provides a general method for the environmentally friendly and biocompatible derivatization of sp3 alkyl halide bonds.

Mild, Efficient and Catalyst‐Free Hydroxylation of Alkyl Halides in Water: Significant Enhancement of Water Nucleophilicity in Dipolar Solvents

AbstractA new and efficient method for the hydroxylation of heteroarylalkyl, arylalkyl and alkyl halides has been developed by exploiting the nucleophilicity of water. The method being operated under neutral conditions, avoids acid/base or metal assisted catalysis. The protocol has been optimized for a range of aqueous aprotic/protic solvents. The new operation is very simple, highly economical, ecofriendly, safest and suitable for acid/base sensitive motifs in yielding the products at high purity.

Simple and green method for synthesis of symmetrical dialkyl disulfides and trisulfides from alkyl halides in water; PMOxT as a sulfur donor

ABSTRACTAn environmentally new, mild and efficient method has been developed for the synthesis of dialkyl disulfides and dialkyl trisulfides in aqueous conditions by a reaction between alkyl halides (and tosylate) and potassium-5-methyl-1,3,4-oxadiazole-2-thiolate (PMOxT) as a sulfur transfer reagent. The advantages of this method are that it occurs under mild reaction conditions, it is base free, it uses water as the solvent and it occurs in high yields. A variety of dialkyl disulfides and dialkyl trisulfides can be obtained in good to excellent yields up to 98%.

Bu4NI‐Catalyzed and tBuOOH‐Oxidized Esterification of Aldehydes with Alkyl Halides in Water

AbstractThe importance of esters has stimulated significant efforts to develop efficient methods for their synthesis. In this study, an oxidative esterification of aldehydes with alkyl halides by using tert‐butyl hydroperoxide as an oxidant, Bu4NI as catalyst, and water as solvent is presented. Notably, this novel esterification protocol is suitable for both aromatic and aliphatic aldehydes, primary and secondary alkyl halides to give ester products with broad structural diversity. Through an intramolecular version of this novel esterification process, an alternative synthetic approach toward the biologically interesting isobenzofuran‐1(3 H)‐one was also realized. Compared with literature procedures, the synthetic strategies developed herein showed advantages such as direct use of commercially available and economical starting materials, wide substrate scope, good tolerance of functional groups, sustainable oxidant, and no need of an inert atmosphere or dry solvents.

Photon can tremendously accelerate the alkyl iodides’ elimination in water

Elimination of the alkyl halides in water is very difficult due to the heterogeneous nature and the limitation of base strength. We discovered that ultra-violet (UV) light can enhance the elimination rate of alkyl iodides, including primary, secondary, and tertiary iodides in water dramatically for the first time. We propose a tandem radical-carbocation reaction mechanism to rationalize this special property of alkyl iodides.

Dehalogenation of Functionalized Alkyl Halides in Water at Room Temperature.

Alkyl bromides and chlorides can be reduced to the corresponding hydrocarbons utilizing zinc in the presence of an amine additive. The process takes place in water at ambient temperatures, enabled by a commercially available designer surfactant. The reaction medium can be readily recycled, and the amount of organic solvent invested for product isolation is minimal, leading to very low E Factors.

ChemInform Abstract: A Novel and Efficient Synthesis of Alkyl Thiocyanates from Alkyl Halides in Water Using Phase Transfer Catalysts.

AbstractBoth BPC and BPS are successfully applied to the reaction of primary alkyl halides with KSCN.

ChemInform Abstract: Cross‐Coupling of Alkyl Halides with Heteroaromatic Halides, in Water at Room Temperature.

AbstractOrgano zinc halides, readily generated from water‐insoluble hetaryl bromides, react under optimized conditions with a variety of alkyl halides in water using a hydrophilic Pd‐catalyst and a commercially available amphiphilic phase transfer catalyst.

A novel and efficient synthesis of alkyl thiocyanates from alkyl halides in water using phase transfer catalysts

1,4-Bis(triphenylphosphonium)-2-butene dichloride (BTPBDC) and 1,4-bis(triphenyl phosphonium)-2-butene dithiocyanate (BTPBDT) were prepared and used as phase-transfer catalysts. Alkyl halides were converted efficiently to the corresponding alkyl thiocyanates under mild reaction conditions in water. No evidence for the formation of isothiocyanates as by-product of the reaction was observed.

ChemInform Abstract: Stereoselective Negishi‐Like Couplings Between Alkenyl and Alkyl Halides in Water at Room Temperature.

AbstractThe procedure is very simple and the reaction proceeds mostly with retention of the stereoconfiguration of the alkenes.

Stereoselective Negishi-like couplings between alkenyl and alkyl halides in water at room temperature.

Mix in water and then stir. That is all that is required in this new approach to stereoselective sp(3)-sp(2) cross-couplings between an alkyl and alkenyl halide. Prior formation of organozinc reagents is not required.

Indium (Zinc)−Copper-Mediated Barbier-Type Alkylation Reaction of Nitrones in Water: Synthesis of Amines and Hydroxylamines

An efficient method for the Barbier-type alkylation reaction of various nitrones (including chiral version) and alkyl halides in water is described. The amines and hydroxylamines can be obtained in good yields, depending on the judicious choice of the metal complexes used.

Highly efficient synthesis of thioesters in water

Thioesters were efficiently prepared via the direct reaction of tertiary thioamides and alkyl halides in water, and in the presence of catalytic amounts of NaI, hexadecyltrimethylammonium bromide (HTAB), and 1,4-diazabicyclo[2.2.2]octane (DABCO). Hence, thioamides smoothly undergo an S-alkylation with alkyl halides in aqueous media following by hydrolysis to afford the corresponding thioesters in very good to excellent yields.

ChemInform Abstract: Triethylamine‐Catalyzed One‐Pot Synthesis of Trithiocarbonates from Carbon Disulfide, Thiols, and Alkyl Halides in Water.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Indium—Copper and Indium—Silver Mediated Barbier—Grignard‐Type Alkylation Reaction of Aldehydes Using Unactivated Alkyl Halides in Water

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Indium−Copper and Indium−Silver Mediated Barbier–Grignard-Type Alkylation Reaction of Aldehydes Using Unactivated Alkyl Halides in Water

An efficient method has been developed for the Barbier-Grignard-type alkylation reaction of aldehydes (including aliphatic version) using unactivated alkyl halides in water in the presence of an In/CuI/I(2) or In/AgI/I(2) system. The reactions proceeded more efficiently in water than in organic solvent. In, CuI or AgI, and I(2) were all essential for the efficient progress of the reactions. A radical-type reaction mechanism was studied and proposed by using 4-pentenal as substrate.

Triethylamine-catalyzed one-pot synthesis of trithiocarbonates from carbon disulfide, thiols, and alkyl halides in water

Symmetrical and unsymmetrical trithiocarbonates were prepared by a simple and efficient one-pot reaction of thiols, carbon disulfide, and alkyl halides in the presence of triethylamine in water at room temperature.

The Barbier—Grignard‐Type Carbonyl Alkylation Using Unactivated Alkyl Halides in Water.

AbstractFor Abstract see ChemInform Abstract in Full Text.

A Monte Carlo Simulation of the Electrochemical Reduction of Alkyl Halides in Water. On the Validity of Marcus' Relationship

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA Monte Carlo Simulation of the Electrochemical Reduction of Alkyl Halides in Water. On the Validity of Marcus' RelationshipVictor Perez, Jose M. Lluch, and Juan BertranCite this: J. Am. Chem. Soc. 1994, 116, 22, 10117–10123Publication Date (Print):November 1, 1994Publication History Published online1 May 2002Published inissue 1 November 1994https://doi.org/10.1021/ja00101a033RIGHTS & PERMISSIONSArticle Views75Altmetric-Citations15LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (912 KB) Get e-Alerts Get e-Alerts

A water soluble tin hydride reagent

A water soluble tin hydride has been synthesized carrying three methoxyethoxypropyl groups. It reduces various alkyl halides in water, or in organic solvents.