The Quest to Quit: an Exploration of the Cessation - Relapse Cycle of Cigarette Smoking

The smoker's perspective is seldom sought in cessation research. Consequently, cessation approaches may be less effective because they are not based on assumptions and interpretations shared by those who smoke. Understanding how chronic relapsing smokers interpret their predicament could enhance cessation approaches, improving the chances for complete, permanent cessation. To generate such an understanding, five participants were recruited who had attempted to quit smoking several times. Aiming for depth rather than breadth, multiple interviews were conducted with each participant, who also kept an event diary, recording current smoking, nicotine withdrawal, lapsing and relapsing. Narratology, a biographical method of symbolic interactionism drawing on thematic, structural, and dialogic analysis, was used to elicit the participants' points of view from interview and diary data. The findings show that participants make sense of their chronic relapsing through a master narrative of 'willpower versus weakness'. Meanwhile, the tobacco control domain is largely driven by 'cost', and subsidised treatments are driven by the 'addiction' master narrative. This gap between ways of making sense of smoking and relapse can cause self-stigma, reducing the likelihood that quitting will be attempted and that quit attempts will succeed. Changes are proposed to mitigate the negative effects on self-efficacy brought about through the present approach to tobacco control. Ways to improve the effectiveness of existing treatments are suggested. Finally, the value of the narrative method is highlighted, with suggestions for its use in research where elucidating the insider point of view may improve treatment outcomes

A Chelating Nucleophile Plays a Starring Role: 1,8-Naphthyridine-Catalyzed Polycomponent α,α-Difluorination of Acid Chlorides

A dually activated ketene enolate, generated from an acid chloride, the unusual chelating nucleophile (1,8-naphthyridine), and a Lewis acid, reacts to afford a host of α,α-difluorinated products in the presence of a benchtop-stable fluorinating agent (Selectfluor). The use of this method to synthesize otherwise difficult to make products is highlighted along with computational and spectroscopic support for the proposed chelate

Photocatalyzed Benzylic Fluorination: Shedding “Light” on the Involvement of Electron Transfer

The photocatalyzed oxidation of benzylic compounds by 1,2,4,5-tetracyanobenzene (TCB) in the presence of Selectfluor provides a synthetically efficient route to electron deficient, less substituted, and otherwise inaccessible benzylic fluorides. The virtue of this system is multifold: it is metal-free and mild, and the reagents are inexpensive. Mechanistically, the data suggest the intimate formation of intermediate radical cations in the key radical forming step, as opposed to a concerted hydrogen atom transfer process

Intermolecular Aliphatic C–F···H–C Interaction in the Presence of “Stronger” Hydrogen Bond Acceptors: Crystallographic, Computational, and IR Studies

An unprecedented intermolecular aliphatic C–F···H–C interaction was observed in the X-ray crystal structure of a fluorinated triterpenoid. Despite the notion of fluorine being a poor acceptor, computational and IR studies revealed this interaction to be a weak to moderate hydrogen bond with a C–H stretch vibration frequency blue-shifted by 14 cm^–1 and <i>d</i>(F–H) = 2.13 Å. In addition, the aliphatic C–F bond is the preferred acceptor in the presence of multiple, traditionally <i>stronger</i> oxygen-based hydrogen bond acceptors

The Diels–Alder Cyclization of Ketenimines

A Diels–Alder reaction between cyclopentadiene and a variety of ketenimines is reported. A copper(I)-bis(phosphine complex catalyzes the cycloaddition across the CN bond of the ketenimine in a [4 + 2] reaction to give an enamine intermediate that is hydrolyzed upon purification to generate aminoketones

A C–F Bond Directed Diels–Alder Reaction

We demonstrate a C–F bond driven Diels–Alder reaction of a fluorinated dienophile and a borole that shows remarkable diastereoselectivity. The product’s structure was confirmed by X-ray crystallography, revealing an unusual conformation featuring a hypercoordinate boron. Calculations suggest that a B···F interaction instigates the reaction chemistry, the magnitude of which is maximized in the transition statein essence, the B···F distance “yo-yos” from long to short in the transition state and back again to long in the product

The Diels–Alder Cyclization of Ketenimines

A Diels–Alder reaction between cyclopentadiene and a variety of ketenimines is reported. A copper(I)-bis(phosphine complex catalyzes the cycloaddition across the CN bond of the ketenimine in a [4 + 2] reaction to give an enamine intermediate that is hydrolyzed upon purification to generate aminoketones

Sensitized Aliphatic Fluorination Directed by Terpenoidal Enones: A “Visible Light” Approach

In our continued effort to address the challenges of selective sp³ C–H fluorination on complex molecules, we report a sensitized aliphatic fluorination directed by terpenoidal enones using catalytic benzil and visible light (white LEDs). This sensitized approach is mild, simple to set up, and an economical alternative to our previous protocol based on direct excitation using UV light in a specialized apparatus. Additionally, the amenability of this protocol to photochemical flow conditions and preliminary evidence for electron-transfer processes are highlighted

Triethylborane-Initiated Radical Chain Fluorination: A Synthetic Method Derived from Mechanistic Insight

We offer a mild, metal-free sp³ C–H fluorination alternative using Selectfluor and a substoichiometric amount of triethylboranean established radical initiator in the presence of O₂. This radical-chain-based synthetic method is particularly noteworthy as an offspring of the insight gained from a mechanistic study of copper-promoted aliphatic fluorination, constructively turning O₂ from an enemy to an ally. Furthermore, BEt₃/O₂ is a preferred initiator in industrial processes, as it is economical, is low in toxicity, and lends way to easier workup

Synthesis of a Tight Intramolecular OH···Olefin Interaction, Probed by IR, ¹H NMR, and Quantum Chemistry

We have synthesized a molecule containing a tight hydrogen-bonding interaction between an alcohol and a nonconjugated π-system. The strength of this hydrogen bond results in a large red shift, nearly 189 cm^–1, on the alcohol stretching frequency in the IR spectrum in comparison to a free alcohol control. The interaction is notable in that it possesses a better defined intramolecular hydrogen bond compared to the usual molecules for which it is noted, such as <i>syn</i>-7-norbornenol. This interaction was studied through the use of IR and NMR spectroscopy, X-ray crystallography, and molecular modeling calculations