Intermolecular Palladium‐Catalyzed Oxidative Fluorocarbonylation of Unactivated Alkenes: Efficient Access to β‐Fluorocarboxylic Esters

Abstract

An ovel palladium-catalyzed intermolecular oxidative fluorocarbonylation of alkenes has been developed, in which employment of ac ooperative process with electrophilic ArIF 2 -meidated alkenes activation and palladium-catalyzed carbonylation is crucial for the successful catalytic transformation. The current transformation presents the first convenient method to generate b-fluorinated carboxylica cid derivatives under mild reaction conditions from simple alkenes with excellent regioselectivity.

The Chemistry of CO: Carbonylation

“…Liu and co-workers developed several novel procedures for the oxidative carbonylative transformation of alkenes (Scheme 7). [26][27][28] With palladium as the catalyst and hypervalent iodine as a promoter, both terminal and internal alkenes can be effectively transformed under mild reaction conditions. From the point of view of reaction mechanisms, a three-membered iodonium ion intermediate is initially formed after an alkene reacts with hypervalent iodine.…”

Tuning Regioselectivity of Wacker Oxidation in One Catalytic System: Small Change Makes Big Step

“…2-(Pent-4-en-1-yl)isoindoline-1,3-dione (1j). 23 This compound was prepared according to general procedure and purified by silica gel column (PE/EA = 10/1). 1 H NMR (400 MHz, CDCl 3 ) δ 7.86− 7.82 (m, 2 H), 7.73−7.69 (m, 2 H), 5.87−5.77 (m, 1 H), 5.07−4.96 (m, 2 H), 3.70 (t, J = 7.2 Hz, 2 H), 2.12 (q, J = 7.2 Hz, 2 H), 1.82− 1.75 (m, 2 H).…”

Nitromethane-Enabled Fluorination of Styrenes and Arenes

“…Recently, Ritter and co-workers [36][37][38][39] and Sanford's group [40][41][42][43] generated elegantly, transition-metal-catalyzed fluorinated arenes with unreactive N-F reagents. Liu [44][45][46][47][48][49] and Zhang, 50 independently, obtained the significant fluoroamination of styrenes with NFSI via fluoropalladation and copper-catalyzed radical strategy. Li and co-workers 51 reported the fluoroazidation of olefins with Selectfluor and trimethylsilyl azide (TMSN 3 ) in the presence of excess trifluoroacetic acid (TFA).…”