Refernces
10.1002/anie.201204629
The research focuses on the development of a palladium-mediated chemoselective bisallylic alkylation process to synthesize spirocarbocycles, which are cyclic compounds with spiro junctions. The purpose of this study was to explore the chemoselectivity of the reaction, which is heavily influenced by the phosphorous ligand used, and to demonstrate the isomerization of vinylcyclopentenes into cycloheptadienes through a carbon-carbon allylic bond cleavage under mild conditions. The researchers concluded that they had successfully developed a method for the formation of five- and seven-membered carbocycles, with the selectivity of the reaction being dependent on the phosphine ligand. Notably, they observed a rare example of metal-catalyzed ring expansion. Key chemicals used in the process include 1,3-diones, dicarbonate 4, and various phosphine ligands, with [{PdCl(allyl)}2] and PPh3 being the primary catalytic system. The study also involved the use of Xantphos and P(o-C6H4OMe)3, which played a significant role in the formation of cycloheptadiene products. The research concluded with the demonstration of the synthetic potential of vinylcyclopentene substrates and proposed a plausible mechanism for the formation of spirocarbocycles.
10.1021/ja00341a083
The research focuses on the chemistry of trans-fused bicyclo[n.1.O]alkanes and the palladium-catalyzed coupling of acid chlorides and organotins. The purpose of the study was to investigate the isomerization process of compound 2, with a particular interest in the possibility of acid-catalyzed or transition-metal-promoted rearrangement, and to understand the stereochemistry of transmetalation in the palladium-catalyzed coupling process. The researchers concluded that the isomerization of compound 2 did not involve acid-catalyzed processes and that the transmetalation step in the coupling process predominantly occurred with inversion of configuration at the saturated carbon being transferred. Key chemicals used in the process included p-toluenesulfonic acid, acetonitrile, 1,3-cycloheptadiene, phenyltributyltin, benzoyl chloride, and various palladium complexes.
10.1002/cber.19671000321
The study investigates the synthesis and insecticidal properties of seven-ring homologues in the chlordane series. The researchers used Diels-Alder addition reactions involving cycloheptatriene (CHT) and cycloheptadiene (CHD) with hexachlorocyclopentadiene (HCP) to produce tricyclododecene and other seven-ring analogues of chlordane. The structures of these compounds were confirmed through reactions, UV, and NMR spectroscopy. The study also explored various reactions and subsequent products of these chlordane homologues, discussing their insecticidal properties. Key compounds synthesized include 1,9.10.11.12.12-hexachlor-tricyclo[7.2.1.02.8]dodecen-(3.10) (3), which was obtained through heating compound 1 in dimethylformamide or xylene, and 1.9.10.11.12.12-hexachlor-tricyclo[7.2.1.02.8]dodecen-(3.10) (3), which was synthesized by heating compound 1 in absolute xylene. The study found that while these seven-ring homologues are similar to chlordane in structure, they exhibit significantly lower insecticidal efficacy, possibly due to the asymmetry of the tricyclododecane framework and increased molecular flexibility compared to the strained cyclopentane ring in chlordane derivatives.
