Palladium‐Catalyzed Perfluoroalkylative Carbonylation of Unactivated Alkenes: Access to β‐Perfluoroalkyl Esters

Abstract

Transition-metal-catalyzed multi-component carbonylation represents an efficient strategy for the preparation of various functionalizedc arbonyl-containing compounds. Herein, we report ag eneral palladium-catalyzed perfluoroalkylative carbonylation of unactivated alkenes using inexpensive and readily available carbon monoxide as the C1 source and perfluoroalkyl halides as the coupling partner.Awide range of phenols and alcohols were transformed into the corresponding b-perfluoroalkyl esters in high yields with broad functional group tolerance and good chemoselectivity.A dditionally,alkylhalides can be utilized as alkoxy source as well to give the desired esters.M oreover,s everal pharmaceutical and bio-active molecules were also suitable substrates for this onepot multi-component carbonylation process to give the targeted products in good yields.

Switchable Radical Carbonylation by Philicity Regulation

“…Building on the special adsorbability of chitin-derived carbon nanofibrous microspheres (CNMs), Lei and Zhang reported a breakthrough method of employing CNMs as a promoter to realize oxidative double radical carbonylation of alkanes for the synthesis of various alkyl α-ketoamides using stoichiometric di- tert -butyl peroxide as the oxidant . In addition to these inspiring studies, numerous other catalytic methods for single or double carbonylation reactions proceeding via ionic or radical pathways have also been reported and extensively studied. − However, to our knowledge, a generally applicable catalytic system that allows for controlled switchable single and double carbonylative formation of value-added products from the same and simple starting materials is still unknown. − …”

Nickel‐Catalyzed Four‐Component Carbonylation of Ethers and Olefins: Direct Access toγ‐Oxy Esters and Amides

“…Therefore, find a balance between reactivity and selectivity is the key for the success of carbonylative multicomponent reactions. Very recently, our group reported a palladium‐catalyzed perfluoroalkylative carbonylation of alkenes and perfluoroalkyl halides for the synthesis of β‐perfluoroalkyl esters [2] . However, limitations including narrow substrate scope and the need of expensive palladium catalyst remaining.…”

Nickel‐Catalyzed Four‐Component Carbonylation of Ethers and Olefins: Direct Access toγ‐Oxy Esters and Amides

“…Very recently, our group reported a palladium-catalyzed perfluoroalkylative carbonylation of alkenes and perfluoroalkyl halides for the synthesis of β-perfluoroalkyl esters. [2] However, limitations including narrow substrate scope and the need of expensive palladium catalyst remaining. Copper catalysts were studied in this area as well and a coppercatalyzed 1,2-trifluoromethylation carbonylation of alkenes was developed.…”