This account describes our quest for controlling the reactivity of organoiron species, and developing an iron catalyst that can efficiently activate a C–H bond substrate possessing directing group, followed by reaction with nucleophiles (magnesium, zinc, boron, or aluminum reagents), electrophiles (alkyl halides, alkanol derivatives, allyl ethers, alkenes, alkynes, chloroamines), another (heter...

The reactions of dppf-nickel(0) with alkyl halides proceed via three-coordinate nickel(0) intermediates the form [Ni(dppf)(L)]. effects identity added ligand (L) on catalyst speciation and rates [Ni(COD)(dppf)] have been investigated using kinetic experiments density functional theory calculations. A series monodentate ligands in attempts to identify trends reactivity. Sterically bulky electron...

Effective risk management and control methods for potentially genotoxic impurities (PGIs), including alkyl halides, are of significant importance in the medicinal (pharmaceutical) sector. The three halides posaconazole PGIs. detection assessment substances is a top priority all regulatory organizations. Quantifying PGIs at trace levels using standard analytical techniques, such as gas chromatog...

Two different approaches have been employed to enhance the reactivity of 1-alkyl-1,2-diphospholes - the introduction of electron-withdrawing groups either at the phosphorus atoms or in the para-position of the arene ring. The alkylation of sodium 1,2-diphospha-3,4,5-triphenylcyclopentadienide with alkyl halides Hal-CH2-R (R = CN, COOEt, OMe, CH2OEt) results in corresponding 1-alkyl-3,4,5-triphe...

Compared to structurally related linear trialkylamines, a simple macrocyclic amine with an anion-binding cavity exhibits very large rate enhancements (>10(5)) for stoichiometric N-alkylation with primary alkyl, allyl, and benzyl halides in the weakly polar solvent CDCl3. There is also a major distortion of the halide leaving-group order. For example, with benzyl halides the relative leaving-gro...

The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as w...

Hydrophobically modified (HM) water-soluble polymers, e.g. cellulose, starch or guar exhibit enhanced solution viscosity and unique rheological behaviour. These properties are explained in terms of intermolecular hydrophobic associations [1]. The general solution viscosity behavior of HM polymers of different hydrophobic chain length (moth frequently in the range of C8 to C24) is characterized ...

A fast and efficient protocol for the synthesis of N,N'-disubstituted urea derivatives from alkyl halides and primary or secondary amines has been developed. The synthetic pathway combines nucleophilic substitutions and a Staudinger-aza-Wittig reaction in the presence of polymer-bound diphenylphosphine under 14 bar of CO2 pressure and has been performed in a one-pot two-step process. The protoc...

Total synthesis of spider toxins HO-416b (1) and Agel-489 (2) was accomplished using the 2-nitrobenzenesulfonamide (Ns) group as both a protecting and activating group. In this strategy, the C-N bonds were constructed by alkylation of sulfonamides with alkyl halides or Mitsunobu reaction with the corresponding alcohol. Beginning with monoprotection of the symmetrical diamine, the construction o...