Iodoamination of Alkenyl Sulfonamides by Potassium Iodide and Hydrogen Peroxide in Aqueous Medium

Abstract

A procedure for the iodoamination of unfunctionalized olefins tethered to a tosyl‐protected NH‐group has been developed. The combined use of KI and H2O2 in aqueous medium was effective for the preparation of iodomethyl‐substituted nitrogen‐containing heterocycles. The selective exo‐trig iodocyclization provided 1,2‐bifunctional 5‐, 6‐, and 7‐membered cyclic skeletons.

Catalyst-Free Visible-Light-Mediated Iodoamination of Olefins and Synthetic Applications

“…Consequently, a broad range of protocols for chloroamination , and bromoamination of unfunctionalized double bonds have been disclosed. However, while impressive work has been published on intramolecular iodoamination yielding various heterocyclic products, the analogous intermolecular ATRA-type iodoamination seems to be far less explored. Recent seminal work describes this basic idea in only limited examples and with difficulties in product isolation .…”

Intramolecular Aminoazidation of Unactivated Terminal Alkenes by Palladium-Catalyzed Reactions with Hydrogen Peroxide as the Oxidant

“…This is likely due to the competitive paths of protonolysis and/or β-hydride elimination that become dominant when the oxidant is incapable of bringing the Pd­(II) complex to the Pd­(IV) oxidation state . With respect to the latter point, reaction of carbamate 1j with the system of PIFA, KI, and NaN 3 provided the cyclization/azidation product 16 as a single diastereoisomer, isolated in 42% yield (Scheme , eq B) . This result confirms that the failure to obtain the aminoazidation products from substrates 1j and 1k (Scheme , entries 9 and 10, respectively) is not due to the intrinsic instability of the final product.…”