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Iron-mediated segment coupling followed by oxidative 1,5/6-hydrogen atom transfer (HAT) for synthesis of ε-oxo alkene derivatives is developed. This transformation involved translocation of the radical from H-to-C-to-C-to-C followed by the oxidation under MHAT conditions providing rapid access to 1,6/1,7-keto functionalized esters/ketone/sulfones/phosphonates/arenes. The different outcomes of coupling with acceptors could be explained by bond dissociation energies (BDEs), and mechanistic insights were gained through control experiments, including deuterium labeling studies.
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http://dx.doi.org/10.1021/acs.orglett.4c03749 | DOI Listing |
Org Lett
November 2024
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Iron-mediated segment coupling followed by oxidative 1,5/6-hydrogen atom transfer (HAT) for synthesis of ε-oxo alkene derivatives is developed. This transformation involved translocation of the radical from H-to-C-to-C-to-C followed by the oxidation under MHAT conditions providing rapid access to 1,6/1,7-keto functionalized esters/ketone/sulfones/phosphonates/arenes. The different outcomes of coupling with acceptors could be explained by bond dissociation energies (BDEs), and mechanistic insights were gained through control experiments, including deuterium labeling studies.
View Article and Find Full Text PDFJ Am Chem Soc
July 2018
State Key Laboratory of Bioorganic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis , Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences , 345 Lingling Road , Shanghai 200032 , China.
Aplysiasecosterol A (1) is a structurally unusual 9,11-secosteroid isolated from the sea hare Aplysia kurodai. We have accomplished the first and asymmetric total synthesis of 1 in a convergent fashion. The left-hand segment bearing three adjacent stereocenters was constructed through desymmetrizing reduction, ketalization, and radical cyclization.
View Article and Find Full Text PDFJACC Cardiovasc Imaging
June 2019
Centro Cardiologico Monzino, IRCCS, Milan, Italy.
Objectives: This study aimed to evaluate the correlation between different haptoglobin (Hp) phenotypes and myocardial infarction characteristics as detected by cardiac magnetic resonance (CMR) in consecutive patients after ST-segment elevation myocardial infarction (STEMI).
Background: Hp is a plasma protein that prevents iron-mediated oxidative tissue damage. CMR has emerged as the gold standard technique to detect left ventricular ejection fraction (LVEF), extent of scar with late gadolinium enhancement (LGE) technique, microvascular obstruction (MVO), and myocardial hemorrhage (MH) in patients with STEMI treated by primary percutaneous coronary intervention (pPCI).
Brain
January 2017
1 German Center for Neurodegenerative Diseases (DZNE), Leipziger Strasse 44, 39120 Magdeburg, Germany.
Although iron-mediated oxidative stress has been proposed as a potential pathomechanism in Parkinson's disease, the global distribution of iron accumulation in Parkinson's disease has not yet been elucidated. This study used a new magnetic resonance imaging contrast, quantitative susceptibility mapping, and state-of-the-art methods to map for the first time the whole-brain landscape of magnetostatic alterations as a surrogate for iron level changes in n = 25 patients with idiopathic Parkinson's disease versus n = 50 matched controls. In addition to whole-brain analysis, a regional study including sub-segmentation of the substantia nigra into dorsal and ventral regions and qualitative assessment of susceptibility maps in single subjects were also performed.
View Article and Find Full Text PDFCaspian J Intern Med
September 2013
Department of Cardiology, Babol University of Medical Sciences, Babol, Iran.
Background: Iron-mediated cardiomyopathy is the main complication of thalassemia major (TM) patients. Therefore, there is an important clinical need in the early diagnosis and risk stratification of patients. The aim of this study was to evaluate the efficacy of tissue doppler imaging (TDI) to study cardiac iron overload in patients with TM using T2* magnetic resonance (MR) as the gold-standard non-invasive diagnostic test.
View Article and Find Full Text PDF