Regio- and Stereoselective Copper-Catalyzed Allylation of 1,3-Dicarbonyl Compounds with Terminal Allenes

Abstract

Simple ligand-free copper systems were found as efficient catalysts for the addition of 1,3-dicarbonyl compounds to N-allenyl derivatives. This highly regio- and stereoselective reaction has been accomplished in the presence of malonates, 1,3-ketoesters, and 1,3-diketones with good to excellent yields under mild conditions. This methodology represents the first allylation of 1,3-dicarbonyl compounds with allenes catalyzed by copper.

Easy Access to Allylic Sulfones Through Transition-Metal-Free Hydrosulfonylation Of Allenes

“…Detailed experimental procedures and characterization data (NMR 1 H, 13 C, 19 F, ESI-HRMS and m.p., if solid) for all new compounds are provided in the supporting information (PDF).…”

“…In our course to build new original allylic structures, we started investigate the C-S bond formation via coppercatalyzed hydrofunctionalization of allenes. After starting with usual conditions described in our previous work for the C-C [11][12][13] , C-N [14][15][16][17] and C-O 18 bonds formation, we quickly realized that the reaction could occur without a transition metal, in the…”

Hydroarylation of N‐Allenyl Derivatives Catalyzed by Copper**

“…Hydrofunctionalization of allenes mainly allowed the selective formation of C–N, C–O, and C–C bond. [ 2,3,5–8 ] The latter being performed through the addition of pronucleophiles such as malonates, [ 9–12 ] nitriles, [ 13–16 ] alkynes, [ 17–19 ] alkenes, [ 20–22 ] and aryl derivatives. The reaction of aromatic compounds with allenes, known as hydroarylation reaction, consists of adding an aryl moiety to a C–C double bond and constitutes a powerful tool to form a Csp 3 –Csp 2 bond in a regio‐ and stereoselective manner.…”

Hydroarylation of N-Allenyl Derivatives Catalyzed by Copper

“…by copper, 5,[31][32][33][34][35][36][37] we began to study the model reaction between N-allenyl-2-pyrrolidinone 1a with 1,3,5trimethoxybenzene 2a under various conditions presented in Table 1. a Reaction conditions: 1a (0.5 mmol), 2a (0.6 to 1 mmol) and catalyst (0.025 to 0.1 mmol) were placed in a screw tube under argon in 1 mL of solvent for 18h at 25 to 100°C.…”

“…Our group described in 2018 the copper-catalyzed allylation of 1,3dicarbonyl pronucleophiles with terminal N-allenyl derivatives, affording highly valuable γ,δ-unsaturated dicarbonyl compounds. 5 Another type of hydrocarbonation of allenes is hydroarylation, which consists in adding an aryl moiety to a C-C double bond to form a Csp3-Csp2 bond.…”