No abstract

An efficient Mn-catalyzed aerobic oxidative hydroxyazidation of olefins for synthesis of β-azido alcohols has been developed. The aerobic oxidative generation of azido radical employing air as the terminal oxidant is disclosed as the key process for this transformation. The reaction is appreciated by its broad substrate scope, inexpensive Mn-catalyst, high efficiency, easy operation under air, and mild conditions at room temperature. This chemistry provides a novel approach to high value-added β-azido alcohols, which are useful precursors of aziridines, β-amino alcohols, and other important N- and O-containing heterocyclic compounds. This chemistry also provides an unexpected approach to azido substituted cyclic peroxy alcohol esters. A DFT calculation indicates that Mn catalyst plays key dual roles as an efficient catalyst for the generation of azido radical and a stabilizer for peroxyl radical intermediate. Further calculation reasonably explains the proposed mechanism for the control of C-C bond cleavage or for the formation of β-azido alcohols.

Conductive hydrogels had demonstrated significant prospect in the field of wearable devices. However, hydrogels suffer from a huge limitation of freezing when the temperature falls below zero. Here, a novel conductive organohydrogel was developed by introducing polyelectrolytes and glycerol into hydrogels. The gel exhibited excellent elongation, self-healing, and self-adhesive performance for various materials. Moreover, the gel could withstand a low temperature of −20 °C for 24 h without freezing and still maintain good conductivity and self-healing properties. As a result, the sample could be applied for motion detection and signal transmission. For example, it can respond to finger movements and transmit network signals like network cables. Therefore, it was envisioned that the effective design strategy for conductive organohydrogels with antifreezing, toughness, self-healing, and self-adhesive properties would provide wide applications of flexible wearable devices.

The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process.

A Pd-catalyzed aerobic oxidative C–H nitration and acylation of arenes with simple and readily available tert-butyl nitrite (TBN) and toluene as the radical precursors has been developed. Molecular oxygen is employed as the terminal oxidant and oxygen source to initiate the active radical reactants. Many different directing groups such as pyridine, pyrimidine, pyrazole, pyridol, pyridylketone, oxime, and azo groups can be employed in these novel transformations. The PdII/PdIV catalytic cycle through a radical process is the most likely pathway for these oxidative C–H nitration and acylation reactions.

Flexible hydrogel-based sensors have attracted significant attention due to promising applications of wearable devices.

An efficient method for the direct preparation of high synthetic valuable α-hydroxycarbonyls is described. The simple and readily available I2 or NBS was used as catalyst. DMSO acts as the oxidant, oxygen source, and solvent. A diverse range of tertiary Csp(3)-H bonds as well as more challenging secondary Csp(3)-H bonds could be hydroxylated in this transformation. The reaction is mild, less toxic and easy to perform.

The photochemical deracemization of spiro[cyclopropane-1,3'-indolin]-2'-ones (spirocyclopropyl oxindoles) was studied. The corresponding 2,2-dichloro compound is configurationally labile upon direct irradiation at l = 350 nm and upon irradiation at l = 405 nm in the presence of achiral thioxanthen-9-one as the sensitizer.T he triplet 1,3-diradical intermediate generated in the latter reaction was detected by transient absorption spectroscopya nd its lifetime determined (t = 22 ms). Using ac hiral thioxanthone or xanthone,w ith al actam hydrogen bonding site as ap hotosensitizer,a llowed the deracemization of differently substituted chiral spirocyclopropyl oxindoles with yields of 65-98 %and in 50-85 %ee(17 examples). Three mechanistic contributions were identified to co-act favorably for high enantioselectivity:t he difference in binding constants to the chiral thioxanthone,t he smaller molecular distance in the complex of the minor enantiomer, and the lifetime of the intermediate 1,3-diradical.