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Hoarding disorder (HD) is characterised by excessive acquisition and distress associated with discarding objects, resulting in significant clutter. At present, cognitive behavioural therapy (CBT) represents the strongest evidence base for treating HD, although some limitations exist. Little research has examined the effectiveness of remote-CBT interventions for HD in older adults. This case study focuses on Mary, an older female adult presenting with clinically significant hoarding behaviours which severely impact her daily functioning and quality of life. Assessment and intervention followed a structured CBT approach. Despite the complicating factor of COVID-19, Mary responded well to a remote-CBT intervention, with progress indicators suggesting modest improvements in personal, social and occupational functioning. These findings support the use of remote-CBT for HD in both reducing frequency and intensity of hoarding behaviours and improving wellbeing. Key learning aims (1) Hoarding disorder (HD) is a poorly understood disorder that can significantly impact an individual’s personal, social and occupational functioning. (2) According to a cognitive behavioural model, HD emanates from information-processing deficits, emotional attachment difficulties, behavioural avoidance and maladaptive beliefs about objects and the self (Frost and Hartl, 1996). (3) Observations from this case study suggest the acceptability and effectiveness of a remote cognitive behavioural therapy (CBT) intervention for HD, with outcomes appearing congruous with those produced by face-to-face intervention. (4) While research attests to the effectiveness of a CBT intervention for HD, an augmented account of the mechanisms through which these outcomes are achieved is required.

The intermolecular thiol-ene reaction is emerging as a highly efficient; free-radical mediated “click” process with diverse applications in biofunctionalisation and materials science. The related intramolecular thiol-ene reactions offer significant potential for the preparation of a wide range of sulphur containing heterocycles including synthetic therapeutics such as cyclic peptides and thiosugars. Herein, we review recent advances in intramolecular thiyl-radical mediated reactions and their applications for synthetic and medicinal chemistry.

A novel intramolecular thiol-yne cyclisation strategy has been developed for the synthesis of thioglycals. Both ionic and radical mediated cyclisation pathways have been investigated for D- and L-sugars. The ionic cyclisation provides exclusive access to 5-exo products directly from the thioesters whereas the radical cyclisation provides access to both 5-exo and 6-endo products upon photochemical irradiation of the free thiols. These are the first examples of intramolecular thiol-yne cyclisation reactions applied to thiosugar synthesis.

The use of intramolecular thiyl radical cyclizations for the synthesis of thiosugars has been investigated, and a new free-radical-based methodology for the synthesis of biologically important thiosugars has been developed. The methodology is mild and proceeds via either 6-endo or 5-exo cyclization to furnish the thiosugar ring. This represents the first examples of thiyl radical cyclization being applied to the synthesis of thiosugars.

Review: recent advances in intramolecular thiyl-radical mediated reactions and their aplications for synthetic and medicinal chemistry; 49 refs.

The application of thiyl-radical-mediated 5-exo-trig cyclization reactions for the preparation of a series of C-linked 4-thiofuranoside sugars has been investigated. The cyclization reactions were found to proceed in high yield with complete regioselectivity and moderate to excellent diastereoselectivity for a number of benzyl-protected precursors. The diastereoselectivity of the radical cyclization was determined by a number of factors, primarily the stereochemistry at the C-2 position and the nature of the substituents attached to the olefin. The cyclization reactions proceed via transition-state intermediates that favor formation of the 1,2-trans products. For d-sugars, a chairlike transition state is proposed. For l-sugars, both chair- and boatlike transition states could be considered. Inversion of the stereochemistry at C-4 also induced a significant effect on the diastereoselectivity of the radical process. The synthetic route is general for both d- and l-sugars and offers a highly novel and effici...

The application of thiyl-radical-mediated 5-exo-trig cyclization reactions for the preparation of a series of C-linked 4-thiofuranoside sugars has been investigated. The cyclization reactions were found to proceed in high yield with complete regioselectivity and moderate to excellent diastereoselectivity for a number of benzyl-protected precursors. The diastereoselectivity of the radical cyclization was determined by a number of factors, primarily the stereochemistry at the C-2 position and the nature of the substituents attached to the olefin. The cyclization reactions proceed via transition-state intermediates that favor formation of the 1,2-trans products. For D-sugars, a chairlike transition state is proposed. For L-sugars, both chair- and boatlike transition states could be considered. Inversion of the stereochemistry at C-4 also induced a significant effect on the diastereoselectivity of the radical process. The synthetic route is general for both D- and L-sugars and offers a highly novel and efficient strategy for accessing C-linked 4-thiofuranosides. A fluorescently labeled thiosugar was prepared as a putative glycosidase inhibitor.

The use of intramolecular thiyl radical cyclizations for the synthesis of thiosugars has been investigated, and a new free-radical-based methodology for the synthesis of biologically important thiosugars has been developed. The methodology is mild and proceeds via either 6-endo or 5-exo cyclization to furnish the thiosugar ring. This represents the first examples of thiyl radical cyclization being applied to the synthesis of thiosugars.