High prevalence of suicidal ideation in AF: influence of psychology, AF symptom severity and AF burden

Chemoselective Oxidation of Equatorial Alcohols with N-Ligated λ3-Iodanes

“…This would also benefit the broader application of N-HVIs because these reagents can be moisture-sensitive and prone to degradation upon prolonged storage. 9 The initial application of our standard conditions for N-HVI synthesis using TMSOTf, followed by the addition of the substrate, resulted in variable yields of 7 along with significant amounts of silyl-protected 6. The use of the bulkier TBSOTf as the silyl activator suppressed alcohol protection, and a screen of hydrogen bonding and Brønsted acid additives 8,9,[16][17][18] found that the use of AcOH gave a consistently excellent yield of 7 (Scheme 2).…”

“…Recently, our laboratory has reported on the synthetic applications of (bis)cationic nitrogenligated λ 3 -iodanes [PhI-(het) 2 ]2OTf − , or N-HVIs (1) (Scheme 1). [6][7][8][9] Whereas N-HVIs have been known for over 20 years, reports on the synthetic utility of these reagents are scarce. 6,10,11 N-HVIs possess two datively bound heterocyclic nitrogen ligands on the central iodine, resulting in significantly enhanced oxidation potentials relative to traditional λ 3iodanes and opening up new modes of reactivity to this reagent class.…”

“…11,12 Adding to their appeal, N-HVIs are readily synthesized from commercially available PhI(OAc) 2 using just TMSOTf and the desired heterocycle (Scheme 1A), leading to free-flowing white solids. 6 During our recent efforts to develop an electrophilic ring expansion of secondary alcohols with N-HVIs (2 → 3, Scheme 1B), 9 we observed that the relative alcohol stereochemistry had a significant effect on the reaction pathway. In using model substrate 2-Mecyclohexanol (2), cis-2 gave a clean rearrangement to cyclic ether 3, whereas trans-2 led to significant amounts of competitive ketone formation (4).…”