Iodosobenzene-Mediated Three-Component Selenofunctionalization of Olefins

Abstract

A three-component reaction of olefin, diselenide and water, alcohols, phenol, carboxylic acid, or amine by a commercially available hypervalent iodine(III) reagent, PhIO, was developed. This method provides access to a wide range of vicinally functionalized selenoderivatives under ambient conditions with mostly excellent yields and high diastereoselectivity. The developed reaction displays high levels of functional group compatibility and is suitable for the late-stage functionalization of styrenefunctionalized biomolecules. Preliminary investigations on the mechanism of the reaction are also presented.

Selective Difunctionalization of Unactivated Aliphatic Alkenes Enabled by a Metal–Metallaaromatic Catalytic System

“…Examples of the use of a primary amine and unactivated alkenes to construct αamino selenides are few, and this remains a challenge. 26,27,38 In our case, this strategy is compatible with both primary and secondary amines, suggesting that it is a useful complement to existing approaches. We next evaluated nucleophiles, including carboxylic acid and alcohols.…”

“…Difunctionalization of alkenes is a powerful tool for rapid development of structural complexity from simple and abundant feedstock chemicals in a single step. , A commonly used method is transformation of the alkene into a carbocationic intermediate which is subsequently trapped by a nucleophile . Unactivated alkenes, however, often suffer from poor reactivity, and their reactions with oxyacid and Lewis basic amine-based nucleophiles usually have a limited substrate scope. − Transition metal catalyzed amino-difunctionalization of unactivated alkenes in particular is challenging. This is often attributed to the strong coordination of amine donors with metal sites, a liability to oxidation, or poor compatibility under the prevailing reaction conditions. − Thus, a general and practical catalytic approach would be valuable and is in high demand.…”

“…The introduction of both selenium- and nitrogen-containing functional groups into alkenes is potentially important in the synthesis of pharmaceuticals. , In spite of successfully developed aminoselenation methods which use stoichiometric quantities of oxidants or additives, the scope of this reaction is limited to secondary amines. Examples of the use of a primary amine and unactivated alkenes to construct α-amino selenides are few, and this remains a challenge. ,, In our case, this strategy is compatible with both primary and secondary amines, suggesting that it is a useful complement to existing approaches.…”

Updates on hypervalent-iodine reagents: metal-free functionalisation of alkenes, alkynes and heterocycles

“…The title transformation shows good functional group compatibility and is suitable for the late-stage functionalisation of diverse styrene functionalised biomolecules (Scheme 10). 60…”

“…The title transformation shows good functional group compatibility and is suitable for the late-stage functionalisation of diverse styrene functionalised biomolecules (Scheme 10). 60 The initial reaction begins with the oxidation of Ph An efficient method for selective N-and O-arylation of pyridin-2-ones (17) with diaryliodonium salts was reported by Onomura et al, in 2020. This metal-free formation of N-arylated or O-arylated products was highly base dependent.…”