Electrochemical synthesis of polysubstituted sulfonated
pyrazoles
from enaminones and sulfonyl hydrazides was established under metal-free,
exogenous-oxidant-free, and mild conditions. By judicious choice of
different electrochemical reaction conditions, NH
2-functionalized enaminones or N,N-disubstituted enaminones can react with aryl/alkyl sulfonyl
hydrazides to afford tetra- or trisubstituted sulfonated pyrazoles
in moderate to good yields, respectively. The gram-scale electrochemical
transformation demonstrated the efficiency and practicability of this
synthetic strategy. In addition, the sulfonated NH-pyrazole can be obtained via the dissociation of the N-tosyl group. Mechanistic studies reveal that the electrochemical
cascade reaction synthesis of polysubstituted sulfonated pyrazoles
proceeded via the sequence of intermolecular condensation, radical–radical
cross coupling sulfonylation, and pyrazole annulation.
A facile and efficient strategy for the synthesis of 1,4-dihydropyridazines and pyridazines through I2-promoted [4+2] cycloaddition of hydrazones with enaminones has been developed. The switch in selectivity is attributed to...
Given the unique properties of sewage sludgederived carbonaceous materials (SC) and the correlation of SC with recycling sewage sludge in an efficiently safe way, there is significant attraction from researchers to develop innovative methodologies that enable a more extensive application of SC. Applying SC in forming rather than cleaving chemical bonds is highly desirable to maximize the value of sewage sludge. Here, we report the surface-modified SC-catalyzed N−H insertion reaction of a wide range of α-aryl diazoesters with amines, which was first accomplished with moderate to good yield (86%). The catalytic performance of this catalyst is shown by a 10 gram-scale reaction and the synthesis of a drug molecule, (±)-clopidogrel. A mechanistic study suggests that the C−N bond formation involves ammonium ylide intermediates and hydrogen bonding. This discovery leads to the realization of a feasible strategy for sewage sludge recycling and a new avenue to catalyst research.
hexanes are an important class of nitrogencontaining heterocycles that have been found to be key structural features in a wide range of biologically active natural products, drugs, and agrochemicals. As a cutting-edge area, the synthesis of these derivatives has made spectacular progress in recent decades, with various transition-metal-catalyzed and transition-metal-free catalytic systems being developed. In this review, we provide an overview of recent advances in the efficient methods for the synthesis of 3-azabicyclo[3.1.0]hexane derivatives since 2010, emphasizing the scope of substrates and synthesis' applications, as well as the mechanisms of these reactions.
Purpose Fournier’s gangrene is a life-threatening infection which require prompt recognition, early surgical debridement of unhealthy tissue, and initiation of broad-spectrum antibiotics. Relook debridement are usually performed until all the devitalized tissue has been removed. Involvement of the anal sphincter may result in significant morbidity such as permanent incontinence. Dynamic reconstruction of the anal sphincter has always been one of the holy grails in the field of pelvic reconstruction. Method We demonstrate a new method of camera shutter style double-opposing gracilis muscle flaps that allows dynamic sphincteric function without the need for electrostimulation. With biofeedback training, the patient is able to regain dynamic continence, and return to function without a stoma.Results The patient was able to reverse his stoma 13 months after the initial insult and reconstruction with biofeedback training without the use of electrostimulation. ConclusionWith the inset of bilateral gracilis muscle flap in a double opposing, camera shutter fashion around the anus, reconstruction of anal sphincter can be successful without the use of electrostimulation. Intensive biofeedback training is required after surgery to achieve an acceptable anal resting and squeeze pressure before the reversal of stoma.
Extravasation injury is a well-known complication of central venous catheter placement, with potential for extensive soft tissue necrosis. Here, we describe the case of a patient who developed a large right chest well soft tissue defect, due to a chest wall abscess from calcium gluconate infusion via a right internal jugular central venous catheter. After multiple debridements, the chest wall defect was reconstructed with a single stage ipsilateral pectoralis major turnover flap, rhomboid skin flap, and inferior nipple transposition to match the contralateral nipple. There was no further infection, no nipple necrosis, and patient regained full range of motion of the ipsilateral shoulder.
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