HYPERVALENT IODINE METHODS FOR CARBON–NITROGEN AND CARBON–CARBON BOND FORMATION
AuthorSousa e Silva, Felipe Cesar
AdvisorWengryniuk, Sarah E.
Committee memberSieburth, Scott McNeill
Permanent link to this recordhttp://hdl.handle.net/20.500.12613/2074
MetadataShow full item record
AbstractCarbon-carbon and carbon-nitrogen bond forming events are essential in chemistry. Although numerous stoichiometric/catalytic methods provided elegant and powerful solutions enabling those processes, the use of scarce/toxic reagents and harsh conditions is still ubiquitous in this field. As a result, extensive research has been conducted in the development of environmentally benign and inexpensive reagents for such transformations, however, general solutions remain a challenge. In this context, one of the focuses of our lab is to enable those processes in a more practical and sustainable fashion by using hypervalent iodine reagents. In this dissertation we demonstrate the synthetic applications of λ3-iodane reagents towards the formation of challenging carbon-carbon and carbon-nitrogen bonds in a complementary way to the methods already reported. Chapter 1 of this dissertation outlines the general electronic structure, geometry, synthesis and reactivity of λ3-iodanes as serves and background regarding these reagents. Chapter 2 highlights the applications of λ3-iodanes to access high-oxidation state transition metals until the year of 2017. This literature review provides detailed information about how λ3-iodanes can be applied to access 1st, 2nd and 3rd row high-oxidation complexes, as well as mechanistic details and synthetic utility of high-valent transition metals. Chapter 3 demonstrates our efforts to generate selective carbon-nitrogen and carbon-carbon products from a high-valent nickel complex. This led to important information of this mechanism adopted by the reaction and how the choice of oxidant can impact 1e- versus 2e- oxidative pathways on “hard” nickel pincer scaffolds. Chapter 4 describes our efforts towards the selective formation of α-C(sp2)-C(sp2) bonds at the α-position of enones via a reductive Iodonium-Claisen rearrangement. We demonstrate the utility of β-pyridinium silyl enol ethers as a platform for direct α-arylation, and how the 2-iodo-aryl-α-arylated enones can be used to access diverse heterocyclic structures. Chapter 5 demonstrates our initial efforts towards the selective C2 or C3 carbon-nitrogen bond formation on indoles. By exposing different indoles to (bis)cationic nitrogen-ligated HVI (N-HVI) reagents we found that selective C2 or C3 C-H indole-pyridinium salts can be formed in good to excellent yield. Although, this project is not finished yet, we anticipate the indole-pyridinium salts generated could serve as platform for accessing diverse piperidines, pyridones and primary amines through straightforward procedures. The combined chapters of this dissertation highlight the applications of λ3-iodanes towards transition metals and emphasize the applications of these reagents to enable challenging C–C and C–N bond formation events. More importantly, this dissertation serves as a guide for future development of the hypervalent iodine field.
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Effects of ambient carbon monoxide on daily hospitalizations for cardiovascular disease: a time-stratified case-crossover study of 460,938 cases in Beijing, China from 2013 to 2017Li, H; Wu, J; Wang, A; Li, X; Chen, S; Wang, T; Amsalu, E; Gao, Q; Luo, Y; Yang, X; Wang, W; Guo, J; Guo, Y; Guo, X (2018-11-26)© 2018 The Author(s). Background: Evidence focused on exposure to ambient carbon monoxide (CO) and the risk of hospitalizations for cardiovascular diseases (CVD) is lacking in developing countries. This study aimed to examine the effect of CO exposure on hospitalizations for CVD in Beijing, China. Methods: A total of 460,938 hospitalizations for cardiovascular diseases were obtained from electronic hospitalization summary reports from 2013 to 2017. A time-stratified case-crossover design was conducted to investigate the association between CO exposure and hospitalizations for total and cause-specific CVD, including coronary heart disease (CHD), atrial fibrillation (AF), and heart failure (HF). Stratified analysis was also conducted by age group (18-64 years and ≥ 65 years) and sex. Results: Linear exposure-response curves for the association between ambient CO exposure and hospitalizations for CVD was observed. Ambient CO was positively associated with hospitalizations for total CVD and CHD. However, the observed increased risk was not statistically significant for hospitalizations for AF and HF. The strongest effect of CO concentration was observed on the current- and previous-day of exposure (lag 0-1 day). For a 1 mg/m3 increase in a 2-day moving average CO concentration, an increase of 2.8% [95% confidence interval (CI): 2.2 to 3.3%] and 3.0% (95% CI: 2.4 to 3.6%) in daily hospital admissions for CVD and CHD were estimated, respectively. This association was robust after adjusting for other copollutants and did not vary by age group and sex. Conclusions: Ambient CO exposure increased the risk of hospitalizations for CVD, especially for CHD in Beijing. Further studies are warranted to explore the association between ambient CO and hospitalizations for AF and HF.