Generation of allenyliodinanes and their reductive iodonio-Claisen rearrangement

Chemistry of Polyvalent Iodine

“…An alternative procedure consists of a similar tin-iodine(III) and silicon-iodine(III) exchange reaction of (diacetoxyiodo)arenes or iodosylbenzene with tetraphenylstannane699 or trimethylsilylbenzene699 in the presence of boron trifluoride etherate.…”

Dearomative Dual Functionalization of Aryl Iodanes

“…Ochiai et al. have previously explored the reaction of an ortho ‐substituted aryl iodane (2,6‐dimethyl phenyl iodane) with propargyl silane . However, the reaction afforded rearomatized aryl iodide in lieu of the expected dearomatization product.…”

“…A variety of nucleophiles, including allyl/propargyl silanes,– β‐dicarbonyl compounds, 2‐naphthols, difluoroenol silyl ethers, and α‐stannyl nitriles, were found to be suitable for the rearrangement of aryl iodanes. However, the selection of nucleophiles for dearomative rearrangement must meet the following criteria: 1) The rearrangement of aryl iodanes with the nucleophile must take place at low temperature and be complete in a short time so as to avoid the deterioration of the in situ generated dearomative intermediate I , which is likely to be unstable in view of its dearomatized structure with a pendant iodine(III) moiety; 2) the nucleophile must be highly reactive towards aryl iodanes in the rearrangement stage, but completely inactive towards the highly electrophilic dearomative intermediate I so that I can be trapped by the second nucleophile (Nu 2 ; Scheme e); 3) the nucleophile should be a versatile building block to ensure the synthetic utility of the final dearomatization product. Recently, we developed a rapid rearrangement of aryl iodanes with α‐stannyl nitriles (Scheme ) .…”

The Coming of Age in Iodane‐Guided ortho‐C−H Propargylation: From Insight to Synthetic Potential

“…Addressing the first point raised in the introduction, we surmise that the virtual lack of usage of the iodane‐directed propargylation in the last 25 years can be explained by a confluence of factors, including the perceived lack of structural variability accessible for the requisite bis(acyloxy)iodoarenes. Indeed, the original report was largely centered on the simplest iodobenzene and iodotoluene cores . Nevertheless, recent progress, including new methods for ArI(OAc) 2 synthesis, have led to the emergence of bis(acetoxy)iodoarenes as a very versatile aryl λ 3 ‐iodane reagent class ,.…”