Site-Selective Csp3-Csp/Csp3-Csp2 Cross-Coupling Reactions Using Frustrated Lewis Pairs.

The donor-acceptor ability of frustrated Lewis pairs (FLPs) has led to widespread applications in organic synthesis. Single electron transfer from a donor Lewis base to an acceptor Lewis acid can generate a frustrated radical pair (FRP) depending on the substrate and energy required (thermal or photochemical) to promote an FLP into an FRP system. Herein, we report the Csp3-Csp cross-coupling reaction of aryl esters with terminal alkynes using the B(C6F5)3/Mes3P FLP. Significantly, when the 1-ethynyl-4-vinylbenzene substrate was employed, the exclusive formation of Csp3-Csp cross-coupled products was observed. However, when 1-ethynyl-2-vinylbenzene was employed, solvent-dependent site-selective Csp3-Csp or Csp3-Csp2 cross-coupling resulted. The nature of these reaction pathways and their selectivity has been investigated by extensive electron paramagnetic resonance (EPR) studies, kinetic studies, and density functional theory (DFT) calculations both to elucidate the mechanism of these coupling reactions and to explain the solvent-dependent site selectivity.

Tris(pentafluorophenyl)borane-Catalyzed Carbenium Ion Generation and Autocatalytic Pyrazole Synthesis-A Computational and Experimental Study.

In recent years, metal-free organic synthesis using triarylboranes as catalysts has become a prevalent research area. Herein we report a comprehensive computational and experimental study for the highly selective synthesis of N-substituted pyrazoles through the generation of carbenium species from the reaction between aryl esters and vinyl diazoacetates in the presence of catalytic tris(pentafluorophenyl)borane [B(C6 F5 )3 ]. DFT studies were undertaken to illuminate the reaction mechanism revealing that the in situ generation of a carbenium species acts as an autocatalyst to prompt the regiospecific formation of N-substituted pyrazoles in good to excellent yields (up to 81 %).

Triarylborane-Catalyzed Alkenylation Reactions of Aryl Esters with Diazo Compounds.

Herein we report a facile, mild reaction protocol to form carbon-carbon bonds in the absence of transition metal catalysts. We demonstrate the metal-free alkenylation reactions of aryl esters with α-diazoesters to give highly functionalized enyne products. Catalytic amounts of tris(pentafluorophenyl)borane (10-20 mol %) are employed to afford the C=C coupled products (31 examples) in good to excellent yields (36-87 %). DFT studies were used to elucidate the mechanism for this alkenylation reaction.

B(C6F5)3-Catalyzed Diastereoselective and Divergent Reactions of Vinyldiazo Esters with Nitrones: Synthesis of Highly Functionalized Diazo Compounds.

Herein we report a mild, transition-metal-free, highly diastereoselective Lewis acid catalyzed methodology toward the synthesis of isoxazolidine-based diazo compounds from the reaction between vinyldiazo esters and nitrones. Interestingly, the isoxazolidine products were identified to have contrasting diastereoselectivity to previously reported metal-catalyzed reactions. Furthermore, the same catalyst can be used with enol diazo esters, prompting the formation of Mukaiyama-Mannich products. These diazo products can then be further functionalized to afford benzo[b]azepine and pyrrolidinone derivatives.

Borane catalysed cyclopropenation of arylacetylenes.

Triarylboranes have gained substantial attention as catalysts for C-C bond forming reactions due to their remarkable catalytic activities. Herein, we report B(C6F5)3 catalysed cyclopropenation of a wide variety of arylacetylenes using donor-acceptor diazoesters. A mild reaction protocol has been developed for the synthesis of functionalised cyclopropenes (33 examples) in good to excellent yields.