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Alkylating Reagents (alkylating + reagent)

Distribution by Scientific Domains

Chemistry	100%

Selected Abstracts

Palladium(II)-Catalyzed Domino Reaction of 2-(1-Alkynyl)-2-alken-1-ones with Nucleophiles: Scope, Mechanism and Synthetic Application in the Synthesis of 3,4-Fused Bicyclic Tetrasubstituted Furans

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2009
Yuanjing Xiao
Abstract Described herein is the development of a palladium(II)-catalyzed two- or three-component reaction of 2-(1-alkynyl)-2-alken-1-ones with nucleophiles and allylic chlorides. Various types of nucleophiles such as O- , N- , C -based nucleophiles and olefin-tethered O- , N- , C -based nucleophiles were investigated. The scope, mechanism and application of this Pd(II)-catalyzed domino reaction were studied. In these transformations, the palladium catalyst exhibits a dual role, serving simultaneously as a Lewis acid and a transition metal. Two possible reaction pathways (cross-coupling reaction vs. Heck reaction) from the same intermediate furanylpalladium species were observed. The reaction pathway is dependent on the property of the nucleophile and the length of the tethered chain as well. When olefin-tethered O -based nucleophiles were used, only the cross-coupling reaction pathway was observed, in contrast, both reaction pathways were observed when olefin-tethered C -based nucleophiles were employed. The product ratio is dependent on the length of the tethered chain. Furthermore, ring-closing metathesis (RCM) of corresponding furans with CC bonds provides an easy method for the preparation of functionalized oxygen-heterocycles , 3,4-fused bicyclic furans. It is also noteworthy that allylic chloride can be as an oxidant besides its well known function as an alkylating reagent. [source]

Characterizing closely spaced, complex disulfide bond patterns in peptides and proteins by liquid chromatography/electrospray ionization tandem mass spectrometry

JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 1 2002
Ten-Yang Yen
Abstract Identifying the Cys residues involved in disulfide linkages of peptides and proteins that contain complex disulfide bond patterns is a significant analytical challenge. This is especially true when the Cys residues involved in the disulfide bonds are closely spaced in the primary sequence. Peptides and proteins that contain free Cys residues located near disulfide bonds present the additional problem of disulfide shuffling via the thiol,disulfide exchange reaction. In this paper, we report a convenient method to identify complex disulfide patterns in peptides and proteins using liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) in combination with partial reduction by tris(2-carboxyethyl)phosphine (TCEP). The method was validated using well-characterized peptides and proteins including endothelin, insulin, ,-conotoxin SI and immunoglobulin G (IgG2a, mouse). Peptide or protein digests were treated with TCEP in the presence of an alkylation reagent, maleimide-biotin (M-biotin) or N -ethylmaleimide (NEM), followed by complete reduction with dithiothreitol and alkylation by iodoacetamide (IAM). Subsequently, peptides that contained alkylated Cys were analyzed by capillary LC/ESI-MS/MS to determine which Cys residues were modified with M-biotin/NEM or IAM. The presence of the alkylating reagent (M-biotin or NEM) during TCEP reduction was found to minimize the occurrence of the thiol,disulfide exchange reaction. A critical feature of the method is the stepwise reduction of the disulfide bonds and the orderly, sequential use of specific alkylating reagents. Copyright © 2001 John Wiley & Sons, Ltd. [source]

Kinetic study of the reaction of dimethyl carbonate with trialkylamines

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 4 2010
Duane E. Weisshaar
Quaternary ammonium compounds are produced worldwide in hundreds of millions of pound volume annually for a plethora of end-uses from fabric-care formulations to asphalt emulsifiers, typically from nongreen alkylating reagents. The kinetics of a reaction employing dimethyl carbonate (DMC) as a green alkylating agent was investigated using three trialkylamines (tributylamine, trihexylamine, and trioctylamine) at several temperatures. Arrhenius and Eyring analysis of the data showed that values of Ea (79 kJ/mol), ,H, (75 kJ/mol), and ,S, (220 J/(mol K)) were the same for all three amine reactants, consistent with a report that Ea is independent of alkyl chain length when the chain length is greater than three carbons. Although rates are significantly slower with DMC than with other alkylating reagents, the resulting methyl carbonate anion has advantages for clean anion metathesis, which is important for some applications, especially those involving ionic liquids. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 221,225, 2010 [source]

Characterizing closely spaced, complex disulfide bond patterns in peptides and proteins by liquid chromatography/electrospray ionization tandem mass spectrometry

The "Borrowing Hydrogen Strategy" by Supported Ruthenium Hydroxide Catalysts: Synthetic Scope of Symmetrically and Unsymmetrically Substituted Amines

CHEMISTRY - A EUROPEAN JOURNAL, Issue 24 2010
Kazuya Yamaguchi Dr.
Abstract The N -alkylation of ammonia (or its surrogates, such as urea, NH4HCO3, and (NH4)2CO3) and amines with alcohols, including primary and secondary alcohols, was efficiently promoted under anaerobic conditions by the easily prepared and inexpensive supported ruthenium hydroxide catalyst Ru(OH)x/TiO2. Various types of symmetrically and unsymmetrically substituted "tertiary" amines could be synthesized by the N -alkylation of ammonia (or its surrogates) and amines with "primary" alcohols. On the other hand, the N -alkylation of ammonia surrogates (i.e., urea and NH4HCO3) with "secondary" alcohols selectively produced the corresponding symmetrically substituted "secondary" amines, even in the presence of excess amounts of alcohols, which is likely due to the steric hindrance of the secondary alcohols and/or secondary amines produced. Under aerobic conditions, nitriles could be synthesized directly from alcohols and ammonia surrogates. The observed catalysis for the present N -alkylation reactions was intrinsically heterogeneous, and the retrieved catalyst could be reused without any significant loss of catalytic performance. The present catalytic transformation would proceed through consecutive N -alkylation reactions, in which alcohols act as alkylating reagents. On the basis of deuterium-labeling experiments, the formation of the ruthenium dihydride species is suggested during the N -alkylation reactions. [source]