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

Abstract

Apalladium-catalyzed intermolecular arylcarbonylation of unactivated alkenes has been developed. Unsymmetrical diaryliodonium salts (DAISs) were used as arylation reagents,t he bulkya ryl group (Ar L )o fw hich was exclusively incorporated into the arylcarbonylated products,w hich contained the Ar L group and acarboxylic ester group at the a-and b-carbon position, respectively,o ft he original terminal CÀC double bond. The reaction features excellent chemo-and regioselectivity,high functional-group tolerance,and very mild reaction conditions. Scheme 1. Transition-metal-catalyzed arylation of alkenes with unsymmetrical DAISs.

Palladium-catalyzed intermolecular alkynylcarbonylation of unactivated alkenes: easy access to β-alkynylcarboxylic esters

“…13 Meanwhile, we have also demonstrated a palladium-catalyzed arylcarbonylation of unactivated alkenes with diaryliodonium salts as arylation reagents, which involved an aryl–Pd II species generated through oxidation of Pd(0) by diaryliodonium salts. 14 Inspired by this study, we envisioned that, if EBX reagents were used instead of diaryliodonium salts to generate an alkynyl–Pd( ii ) intermediate, the alkynylcarbonylation reaction might be accessible to afford β-alkynylcarbonyl compounds.…”

Nickel/photoredox dual catalyzed arylalkylation of nonactivated alkenes

“…The establishment of efficient protocols for the dicarbofunctionalization in one step is of sustaining passion in organic synthesis to improve the molecular complexity. Alkenes are abundant and ubiquitous motifs that are extensively utilized for conventional dicarbofunctionalization [1][2][3][4][5][6][7][8][9][10] . Along with the rapid development of visible-light-mediated photochemistry [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] , the photoredox reagent has been applied as a synergetic catalyst to participate in the transition-metal catalytic cycle, giving access to emerging reaction manifolds [27][28][29][30] .…”

Constructing chiral bicyclo[3.2.1]octanes via palladium-catalyzed asymmetric tandem Heck/carbonylation desymmetrization of cyclopentenes

“…T ransition-metal (TM)-catalyzed carbonylation reaction [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] , especially palladium-catalyzed tandem Heck/carbonylation reaction, presents an efficient method to construct a variety of synthetically versatile carbonyl compounds from readily accessible organic halides and alkenes [17][18][19][20][21] . Moreover, these methods have been applied as key steps in the total synthesis of natural products and bioactive molecules [22][23][24][25][26][27][28] .…”