Rong Zhao's research while affiliated with Harbin Institute of Technology Shenzhen Graduate School and other places

The introduction of trifluoromethylthio (SCF3) and trifluoromethylseleno (SeCF3) substituents into organic molecules significantly improves the electron‐withdrawing and lipophilic properties of their parent compounds. Therefore, a vast class of versatile reagents were employed to access the corresponding fluorine‐containing compounds. Among them, tetramethylammonium salts, such as (Me4N)SCF3 and (Me4N)SeCF3, have been employed as practical and efficient non‐metal reagents for developing efficient trifluoromethylthiolation and trifluoromethylselenolation in recent years. This Minireview systematically illustrates the application of (Me4N)XCF3 (X=S, Se) in the synthesis of trifluoromethylthiolated and trifluoromethylselenolated compounds, and its content is divided into two categories: transition‐metal‐catalyzed reactions, and transition‐metal‐free reactions.

The utilization of N‐centered radicals to synthesize nitrogen‐containing compounds has attracted considerable attention recently, due to their powerful reactivities and the concomitant construction of C−N bonds. However, the generation and control of N‐centered radicals remain particularly challenging. We report a tethering strategy using SOMO‐HOMO‐converted distonic radical anions for the site‐specific aminations of imidates and amidines with aid of the non‐covalent interaction. This reaction features a remarkably broad substrate scope and also enables the late‐stage functionalization of bioactive molecules. Furthermore, the reaction mechanism is thoroughly investigated through kinetic studies, Raman spectroscopy, electron paramagnetic resonance spectroscopy, and density functional theory calculations, revealing that the aminations likely involve direct homolytic cleavage of N−H bonds and subsequently controllable 1,5 or 1,6 hydrogen atom transfer.

A tethering strategy based on SOMO‐HOMO‐converted dicarboxylate radical anions for site‐specific aminations of imidates and amidines is presented. A variety of β‐ and γ‐amino alcohols and dihydroimidazoles are efficiently prepared in good to excellent yields with high functional‐group tolerance under visible‐light irradiation, and late‐stage functionalization of bioactive molecules is also achieved with non‐covalent interaction patterns. Abstract The utilization of N‐centered radicals to synthesize nitrogen‐containing compounds has attracted considerable attention recently, due to their powerful reactivities and the concomitant construction of C−N bonds. However, the generation and control of N‐centered radicals remain particularly challenging. We report a tethering strategy using SOMO‐HOMO‐converted distonic radical anions for the site‐specific aminations of imidates and amidines with aid of the non‐covalent interaction. This reaction features a remarkably broad substrate scope and also enables the late‐stage functionalization of bioactive molecules. Furthermore, the reaction mechanism is thoroughly investigated through kinetic studies, Raman spectroscopy, electron paramagnetic resonance spectroscopy, and density functional theory calculations, revealing that the aminations likely involve direct homolytic cleavage of N−H bonds and subsequently controllable 1,5 or 1,6 hydrogen atom transfer.

Site‐selective “cut and sew” transformations employing diazo compounds and hypervalent iodine(III) compounds involve the departure of leaving groups, a “cut” process, followed by a reorganization of the fragments by bond formation, a “sew” process. Bearing controllable cleavage sites, diazo compounds and hypervalent iodine(III) compounds play a critical role as versatile reagents in a wide range of organic transformations because their excellent nucleofugality allows for a large number of unusual reactions to occur. In recent years, the combination of diazo compounds and hypervalent iodine(III) reagents has emerged as a promising tool for developing new and valuable approaches, and has met considerable success. In this Minireview, this combination is systematically illustrated with recent advances in the field, with the aim of elaborating the synthetic utility and potential of this concept as a powerful strategy in organic synthesis.

The combination of diazo compounds and hypervalent iodine(III) reagents has recently enabled the development of valuable synthetic approaches. In this Minireview, this reagent combination is systematically illustrated, with the aim of elaborating the synthetic utility and potential of this concept as a powerful strategy in organic synthesis. Abstract Site‐selective “cut and sew” transformations employing diazo compounds and hypervalent iodine(III) compounds involve the departure of leaving groups, a “cut” process, followed by a reorganization of the fragments by bond formation, a “sew” process. Bearing controllable cleavage sites, diazo compounds and hypervalent iodine(III) compounds play a critical role as versatile reagents in a wide range of organic transformations because their excellent nucleofugality allows for a large number of unusual reactions to occur. In recent years, the combination of diazo compounds and hypervalent iodine(III) reagents has emerged as a promising tool for developing new and valuable approaches, and has met considerable success. In this Minireview, this combination is systematically illustrated with recent advances in the field, with the aim of elaborating the synthetic utility and potential of this concept as a powerful strategy in organic synthesis.

A metal‐free method for reduction of cyclic N‐sulfonyl ketimines catalyzed by B(C6F5)3, using commercially available methylphenylsilane as a reducing reagent under mild conditions has been developed. This reductive method was effective, not only providing the expected cyclic N‐Sulfonamides in good to excellent yields, but also showing good functional‐group tolerance. image John Wiley & Sons, Ltd.

A metal-free and base-free Cl3CCN mediated method was developed for the ipso-hydroxylation of arylboronic acids to corresponding phenols, which promoted by key unstable Lewis adduct intermediate. This transformation has broad...

With the flourishing progress of photochemistry, many electron transfer mechanisms are developed to explain interaction of intermediates, such as MLCT, LMCT, and PCET. Diverse alcohols, served as substrates or a...

In-situ generated bromonium-catalyzed and visible-light photocatalytic Achmatowicz rearrangements of furfuryl alcohols by using cyclic diacyl peroxides as oxidants are described. Both protocols feature broad substrate scope, excellent functional group tolerance,...

The combination of cyclic diacyl peroxides with commercially available halide salts as a unique halogenating system is utilized in Hofmann-Lӧffler-Freytag-type reaction. This strategy allows for the formation of N–chloroamides, δ-brominated products and even biologically relevant pyrrolidines under mild conditions in moderate to excellent yields. Meanwhile, the preliminary structure of the in situ formed brominating reagent is investigated by NMR and UV/Vis analysis.