A visible-light-enabled selective oxidation of alcohols to aldehydes has been developed under transitionmetal-free conditions. Utilizing eosin Y as the direct hydrogen-atom transfer (HAT) photocatalyst and molecular oxygen as the terminal oxidant, both aromatic and aliphatic aldehydes could be obtained in moderate to good yields. Using this approach, various quinazolinones, including two real drug molecules, were easily synthesized from the corresponding o-aminobenzamides and alcohols. Scheme 1. Visible-light-enabled selective oxidation of alcohols to aldehydes and synthesis of quinazolinones from alcohols and o-aminobenzamides.
A photoinduced iron-catalyzed ipso-nitration of aryl halides with KNO 2 has been developed, in which aryl iodides, bromides, and some of aryl chlorides are feasible. The mechanism investigations show that the in situ formed iron complex by FeSO 4 , KNO 2 , and 1,10-phenanthroline acts as the light-harvesting photocatalyst with a longer lifetime of the excited state, and the reaction undergoes a photoinduced single-electron transfer (SET) process. This work represents an example for the photoinduced iron-catalyzed Ullmann-type couplings.
A simple and practical method for the one‐pot synthesis of 3‐aryl‐5‐amino‐1,2,4‐thiadiazoles from imidates and thioureas has been developed. The protocol proceeds through sequential base‐mediated nucleophilic addition‐elimination reactions and an I2‐mediated oxidative coupling for the N–S bond formation. The approach employes readily available and nontoxic substrates and a simple workup to provide 3‐aryl‐5‐amino‐1,2,4‐thiadiazoles that have a free or substituted amino group.
A direct strategy for the selective
synthesis of 3-acyl-1,2,4-oxadiazoles
from alkynes and nitriles has been developed under iron(III) nitrate-mediated
conditions. The mechanism includes three sequential procedures: iron(III)
nitrate-mediated nitration of alkynes leads to α-nitroketones,
dehydration of α-nitroketones provides the nitrile oxides, and
1,3-dipolar cycloaddition of nitrile oxides with nitriles produces
3-acyl-1,2,4-oxadiazoles under iron-mediated conditions. Iron(III)
nitrate plays dual roles in the nitration of alkynes and the activation
of nitriles, while the formation of pyrimidine/isoxazole byproducts
can be efficiently inhibited.
Traditional Tibetan medicine (TTM) is an old traditional medical system, which is an effective and natural method of improving physical and mental health, and has been widely spread in the western part of China for centuries. Halenia elliptica (H. elliptica) D. Don, known as “Jiadiranguo” (Tibetan medicine name) is one of the most important herbal medicine in TTM that is from the genus Halenia (family: Gentianaceae). The whole herb can be used as a medicine to treat hepatobiliary diseases and xeransis, and possesses many biological and pharmacological activities including heat clearing, bile benefiting, liver soothing, digestion promoting, blood nursing, detoxification activities, and so on. In modern research, H. elliptica can be used to treat acute or chronic hepatitis, especially hepatitis B. In addition, the chemical compounds of the herb have potent antihepatitis B virus (anti-HBV) activity in vitro. As an important TTM, further studies on H. elliptica can lead to the development of new drugs and therapeutics for various diseases, and more attention should be paid on the aspects of how to utilize it better.
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