Amines are centrally important motifs in medicinal chemistry and biochemistry, and indispensable intermediates and linchpins in organic synthesis. Despite their cross-disciplinary prominence, synthetic access to amine continues to rely on two-electron approaches based on reductions and additions of organometallic reagents, limiting their accessible chemical space and necessitating stepwise preassembly of synthetic precursors. We report herein a homogeneous photocatalytic tricomponent decarboxylative radical-mediated amine construction that enables modular access to α-branched secondary amines directly from the broad and structurally diverse chemical space of carboxylic acids in a tricomponent reaction with aldehydes and aromatic amines.
View Article and Find Full Text PDFDevelopment of photocatalytic systems that facilitate mechanistically divergent steps in complex catalytic manifolds by distinct activation modes can enable previously inaccessible synthetic transformations. However, multimodal photocatalytic systems remain understudied, impeding their implementation in catalytic methodology. We report herein a photocatalytic access to thiols that directly merges the structural diversity of carboxylic acids with the ready availability of elemental sulfur without substrate preactivation.
View Article and Find Full Text PDFChemodivergent construction of structurally distinct heterocycles from the same precursors by adjusting specific reaction parameters is an emergent area of organic synthesis; yet, understanding of the processes that underpin the reaction divergence is lacking, preventing the development of new synthetic methods by systematically harnessing key mechanistic effects. We describe herein cesium carbonate-promoted oxadiaza excision cross-coupling reactions of β-ketoesters with 1,2,3-triazine 1-oxides that form pyridones in good to high yields, instead of the sole formation of pyridines when the same reaction is performed in the presence of other alkali metal carbonates or organic bases. The reaction can be further extended to the construction of synthetically challenging pyridylpyridones.
View Article and Find Full Text PDFSulfinamides are some of the most centrally important four-valent sulfur compounds that serve as critical entry points to an array of emergent medicinal functional groups, molecular tools for bioconjugation, and synthetic intermediates including sulfoximines, sulfonimidamides, and sulfonimidoyl halides, as well as a wide range of other S(iv) and S(vi) functionalities. Yet, the accessible chemical space of sulfinamides remains limited, and the approaches to sulfinamides are largely confined to two-electron nucleophilic substitution reactions. We report herein a direct radical-mediated decarboxylative sulfinamidation that for the first time enables access to sulfinamides from the broad and structurally diverse chemical space of carboxylic acids.
View Article and Find Full Text PDFPlast Reconstr Surg Glob Open
February 2021
We present the case of an 86-year-old woman who suffered full-thickness soft tissue loss secondary to degloving injury to the lower left limb, resulting in an exposed tibia. This patient underwent drilling to create artificial fenestrations in the cortical bone followed by placement of Integra dermal regeneration template. The technique of drilling fenestrations to expose underlying vasculature of cortical bone has not previously been described in its relationship with Integra dermal regeneration templates in large degloving injuries of the lower limb.
View Article and Find Full Text PDFPain management guidelines for burn injury in pregnant women are scarce. Maternal and fetal morbidity and mortality in pregnant burn patients have been shown to be higher than that of the general population, especially in severe burns. Early intervention and interdisciplinary treatment are critical to optimize maternal and fetal outcomes.
View Article and Find Full Text PDFWorld J Otorhinolaryngol Head Neck Surg
June 2018
Objective: To identify the incidence of laryngotracheal stenosis (LTS) in burn patients requiring mechanical ventilation at a regional academic burn center.
Methods: A retrospective review of all burn patients requiring endotracheal intubation or tracheostomy for airway management between 2003 and 2009 was performed. A group of trauma patients requiring similar airway instrumentation during the same period of time was used as a control.
Objective: Injury to the foot and ankle without involvement of the knee, requiring a patient to become non-weight-bearing or even needing amputation, is a common problem resulting from diverse causes, including diabetic foot ulcers and trauma. The patellar tendon bearing orthosis may be a good option for patients who would functionally deteriorate, attempting to live their lives without the use of a leg. This brace was introduced 58 years ago; however, it is under-utilized clinically and under-represented in the literature.
View Article and Find Full Text PDFBackground: Gastric electric stimulation (GES) is used to treat patients with refractory gastroparesis symptoms. However, the effectiveness of GES in clinical practice and the effect of GES on specific symptoms of gastroparesis are not well delineated.
Aims: To determine the effectiveness of GES for treatment for refractory symptoms of gastroparesis, the improvement in specific symptoms of gastroparesis, and clinical factors impacting on outcome.
Because burn care in the United States is regionalized, burn patients are often transported across state lines to receive their burn treatment. The authors hypothesized that there are differences between in-state and out-of-state reimbursement for burn care. This project was conducted by the American Burn Association (ABA) Government Affairs Committee through the ABA Multicenter Trials Group.
View Article and Find Full Text PDFAcute, rapid, and unimpeded increases in intra-abdominal pressure can lead to multiple organ dysfunction defined as the abdominal compartment syndrome (ACS). If this develops in the absence of obvious intra-abdominal injury, it has been termed secondary ACS (2 degrees ACS). Massive fluid resuscitation in the presence of large burns or shock can lead to 2 degrees ACS.
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