Difunctionalization of Styrenes with Perfluoroalkyl and tert-Butylperoxy Radicals: Room Temperature Synthesis of (1-(tert-Butylperoxy)-2-perfluoroalkyl)-ethylbenzene.

A novel strategy for the difunctionalization of styrenes was developed. This synthesis includes the use of electrophilic perfluoroalkyl and tert-butylperoxy radicals and produces (1-(tert-butylperoxy)-2-perfluoroalkyl)ethylbenzene at room temperature, which has been traditionally difficult to synthesize. With at least four radical species included in the transformation, its high chemoselectivity was extraordinary; the results were further elucidated using computational studies. The methodology also holds a good potential for application as a result of its mild reaction conditions, ease of further modification, and insensitivity to moisture and air.

Upgrading Electroresistive Memory from Binary to Ternary Through Single-Atom Substitution in the Molecular Design.

Herein, two molecules based on urea and thiourea, which differ by only a single atom, were designed, successfully synthesized, and fabricated into resistive random-access memory devices (RRAM). The urea-based molecule showed binary write-once-read-many (WORM) storage behavior, whereas the thiourea-based molecule demonstrated ternary storage behavior. Atomic-force microscopy (AFM) and X-ray diffraction (XRD) patterns show that both molecules have smooth morphology and ordered layer-by-layer lamellar packing, which is beneficial for charge transportation and, consequently, device performance. Additionally, the optical and electrochemical properties indicate that the thiourea-based molecule has a lower bandgap and may be polarized by trapped charges, thus the formation of a continuous conductive channel and electric switching occurs at lower bias voltage, which results in ternary WORM behavior. This study, together with our previous work on single-atom substitution, may be useful to tune and improve device performance in the future design of organic memory.

Combination of fluoroalkylation and Kornblum-DeLaMare reaction: a new strategy for the construction of (Z)-ß-perfluoroalkyl enaminones.

A novel strategy has been developed for the highly chemo- and stereo-selective synthesis of (Z)-ß-perfluoroalkyl enaminones from readily available starting materials via a multicomponent radical reaction involving sequential fluoroalkylation and Kornblum-DeLaMare reaction. Notably, this methodology involves the concurrent cleavage of at least three chemical bonds, including two C-F bonds and one C-X (X = Br or I) bond, as well as the formation of three new bonds, including one C=O bond, one C=C bond and one C-N bond, in one pot.

Tetrabutylammonium iodide catalyzed synthesis of allylic ester with tert-butyl hydroperoxide as an oxidant.

A metal-free C-H oxidation for the construction of allylic esters has been developed. The use of a commercially available and inexpensive catalyst and oxidant, and readily available starting materials, coupled with the operational simplicity of the reaction, renders the methodology a useful alternative to other approaches typically employed in the synthesis of allylic esters.

Synthesis of arylketones by ruthenium-catalyzed cross-coupling of aldehydes with arylboronic acids.

The first ruthenium-catalyzed cross-coupling of aldehydes with arylboronic acids is reported. Various aliphatic and aromatic aldehydes are transformed to the corresponding arylketones. A total of 31 examples with moderate to excellent yields are presented, together with the results of an initial mechanistic investigation.

Ruthenium-catalyzed oxidation of alkenes at room temperature: a practical and concise approach to α-diketones.

The catalytic oxidation of alkenes to α-diketones is unprecedented. A new oxidation of alkenes, catalyzed by a ruthenium complex, which allows an efficient route to α-diketones using TBHP as an oxidant is described. This methodology is highly functional group tolerant, is practically convenient, requires no additional ligand, and operates under mild conditions with short reaction times. Based upon experimental observations, a plausible mechanism is proposed.