Understanding and Controlling Fluorinated Diacyl Peroxides and Fluoroalkyl Radicals in Alkene Fluoroalkylations

The demand for practical methods for the synthesis of novel fluoroalkyl molecules is increasing owing to their diverse applications. Our group has achieved efficient difunctionalizing fluoroalkylations of alkenes using fluorinated carboxylic anhydrides as user-friendly fluoroalkyl sources. Fluorinated diacyl peroxide, prepared in situ from carboxylic anhydrides, enables the development of novel reactions when used as a radical fluoroalkylating reagent. In this account, we aim to provide an in-depth understanding of the structure, bonding, and reactivity of fluorinated diacyl peroxides and radicals as well as their control in fluoroalkylation reactions. In the first part of this account, the physical properties and reactivity of diacyl peroxides and fluoroalkyl radicals are described. In the subsequent part, we categorize the reactions into copper-catalyzed and metal-free methods utilizing the oxidizing properties of fluorinated diacyl peroxides. We also outline examples and mechanisms.     

Chemoselective N-acetylation of primary aliphatic amines promoted by pivalic or acetic acid using ethyl acetate as an acetyl donor

The combination of pivalic or acetic acid as a promoter and EtOAc as a solvent and acetyl donor proved to be efficient for the chemoselective N-acetylation of primary aliphatic amines to afford the corresponding acetamides. We developed a simple and convenient approach, which requires mild reaction conditions. Competitive inter- and intramolecular reactions between aliphatic amines, alcohols, and aromatic amines were examined, and chemoselectivity was achieved by adjusting the conditions of the reaction.     

An efficient method for 3,4-dihydroisoquinolinium ion formation,leading to a facile introduction of nucleophiles

The ketene silyl acetal derived from ethyl 2-benzyltetrahydroisoquinoline-1-carboxylate undergoes a rapid oxidation reaction with N-bromosuccinimide to form 3,4-dihydroisoquinolinium ion, which reacts with Grignard reagents to give 1,1-disubstituted tetrahydroisoquinolines in good yields.     

Adsorption and separation behavior of strontium and yttrium using a silica-based bis(2-ethylhexyl) hydrogen phosphate adsorbent

Journal of Radioanalytical and Nuclear Chemistry - (HDEHP?+?Hexa)/SiO2-P, a silica-based adsorbent, was prepared and used to separate Y(III) from a mixed solution of Sr(II) and Y(III)....     

Neural network optimization of material composition of a functionally graded material plate at arbitrary temperature range and temperature rise

Summary A neural network model is applied to optimization problems of material compositions for a functionally graded material plate with arbitrarily distributed and continuously varied material properties in the thickness direction. Unsteady temperature distribution is evaluated by taking into account the bounds of the number of the layers. Thermal stress components for an infinite functionally graded material plate are formulated under traction-free mechanical conditions. As a numerical example, a plate composed of zirconium oxide and titanium alloy is considered. In the optimization problem of minimizing the thermal stress distribution, the numerical calculations are carried out making use of the neural network. The optimum material composition is determined by taking into account the effect of temperature-dependence of material properties. The results obtained by neural network and ordinary nonlinear programming method are compared. Received 3 March 1998; accepted for publication 22 May 1998