A Cooperative Strategy for the Highly Selective Intermolecular Oxycarbonylation Reaction of Alkenes using a Palladium Catalyst

Abstract

A novel method for intermolecular functionalization of terminal and internal alkenes has been designed. The electrophilic reagent, hypervalent iodine, plays a key role in this process by activating the alkene C=C bond for nucleophilic addition of the palladium catalyst. This process generates an iodonium-containing palladium species which undergoes CO insertion. The new approach, intermolecular oxycarbonylaton reactions of alkenes, has been achieved and carried out under mild reaction conditions to produce the corresponding β-oxycarbonylic acids with excellent efficiencies and levels of regio- and diastereoselectivity.

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

“…Several common drug molecules and bioactive compounds (e.g., Rolipram, Baclofin, Phenibut) were prepared by the reaction, which shows the potential synthetic value in organic synthesis. Aminocarbonylation, carboamination, azidocarbonylation, oxycarbonylation, and carbooxygenation of simple alkenes were also achieved to prepare the corresponding functional molecules through palladium catalysis.…”

Palladium‐Catalyzed Intermolecular Arylcarbonylation of Unactivated Alkenes: Incorporation of Bulky Aryl Groups at Room Temperature

“…[11] On the basis of these studies,w ee nvisaged that, if the aforementioned I III reagents were replaced with diaryliodonium salts (DAISs) as arylation reagents,anovel arylcarbonylation of alkenes might be feasible. [11] On the basis of these studies,w ee nvisaged that, if the aforementioned I III reagents were replaced with diaryliodonium salts (DAISs) as arylation reagents,anovel arylcarbonylation of alkenes might be feasible.…”

Palladium‐Catalyzed Intermolecular Arylcarbonylation of Unactivated Alkenes: Incorporation of Bulky Aryl Groups at Room Temperature

“…As part of our continuous efforts toward the difunctionalization of alkenes,r ecently we have demonstrated intermolecular oxy-, azido-, and fluorocarbonylation reactions of unactivated alkenes under aC Oa tmosphere,u sing various hypervalent iodine reagents,such as PhI(OAc) 2 ,ArI(N 3 ), and ArIF 2 . [11] On the basis of these studies,w ee nvisaged that, if the aforementioned I III reagents were replaced with diaryliodonium salts (DAISs) as arylation reagents,anovel arylcarbonylation of alkenes might be feasible.…”