10.1021/jo052400g
The research focuses on the synthesis of substituted 2-cyanoarylboronic esters, which are valuable tools in organic synthesis, particularly for the formation of biaryls through cross-coupling reactions. The study aims to develop efficient protocols for the preparation of these derivatives, addressing the growing demand for diversely substituted arylboronic acid derivatives. The researchers utilized a lithiation/in situ trapping protocol with LTMP/B(O-i-Pr)3 to synthesize the esters from various methoxy-, trifluoromethyl-, fluoro-, chloro-, and bromobenzonitriles. The process resulted in high yields and purities with good regioselectivities. The conclusion of the study is that this method is very efficient for preparing substituted 2-cyanoarylboronic esters, which are known to be effective in Suzuki couplings with aryl halides and carbamoyl chlorides, and can be further transformed into various compounds such as aryltetrazole boronic esters. The research also demonstrated the synthetic utility of these esters through a two-step synthesis of a substituted phenanthridine.
10.1016/0040-4020(82)85032-1
The research investigates the arylation and heteroarylation of β-dicarbonyl compounds through a photostimulated SRN1 reaction. The purpose of the study is to explore new synthetic methods for heterocyclic compounds by extending the scope of the SRN1 reaction, which is known for its efficiency in arylation of monoketones but was previously thought not to occur between aryl halides and monoanions of β-dicarbonyl compounds. The researchers discovered that the presence of a cyano electron-withdrawing group allows high-yield SRN1 reactions to occur with β-dicarbonyl derived monoanions. Key chemicals used in the research include bromobenzonitriles, bromocyanopyridine, and various β-dicarbonyl compounds such as malonates, ethyl-cyanoacetate, and 2,4-pentanedione. The study concludes that the SRN1 reaction mechanism is supported by experimental observations, including the necessity of photostimulation and the influence of the cyano group's strong withdrawing effect on the reactivity. The research demonstrates that the SRN1 reaction can be efficiently applied to introduce aryl groups onto β-dicarbonyl compounds, offering a versatile and high-yield synthetic method for a variety of heterocyclic compounds.