6491-93-6Relevant academic research and scientific papers
Gold-Mediated Isomerization of Cyclooctyne to Ring Fused Olefinic Bicycles
Das, Animesh,Hua, Yuanda,Yousufuddin, Muhammed,Cundari, Thomas R.,Jeon, Junha,Dias, H.V. Rasika
, p. 995 - 1001 (2016)
Isomerization reactions of cyclooctyne mediated by N-heterocyclic carbene supported gold(I) leading to ring-contraction and the formation of 5/5-fused bicyclic alkenes have been observed. Isolation and complete characterization, including X-ray structural data of the cationic gold(I) complexes featuring the precursor alkyne and the product alkenes are also described. Gold catalyzes the isomerization of cyclooctyne leading to alkenes featuring two fused five-membered rings.
Vinyl Carbocations Generated under Basic Conditions and Their Intramolecular C-H Insertion Reactions
Wigman, Benjamin,Popov, Stasik,Bagdasarian, Alex L.,Shao, Brian,Benton, Tyler R.,Williams, Chloé G.,Fisher, Steven P.,Lavallo, Vincent,Houk,Nelson, Hosea M.
supporting information, p. 9140 - 9144 (2019/06/08)
Here we report the surprising discovery that high-energy vinyl carbocations can be generated under strongly basic conditions, and that they engage in intramolecular sp3 C-H insertion reactions through the catalysis of weakly coordinating anion salts. This approach relies on the unconventional combination of lithium hexamethyldisilazide base and the commercially available catalyst, triphenylmethylium tetrakis(pentafluorophenyl)borate. These reagents form a catalytically active lithium species that enables the application of vinyl cation C-H insertion reactions to heteroatom-containing substrates.
Oxidative C(sp3)-H bond cleavage, C-C and CC coupling at a boron center with O2 as the oxidant mediated by platinum(II)
Pal,Zavalij,Vedernikov
supporting information, p. 5376 - 5378 (2014/05/06)
Dimethyl- and diphenylplatinum(II) fragments PtIIR2 (R = Me, Ph) enable facile and efficient oxidative C(sp3)-H bond cleavage and stepwise C-C and C=C coupling at the boron atom of a coordinated 1,5-cyclooctanediyldi(2-pyridyl)borato ligand with O2 as the sole oxidant. the Partner Organisations 2014.
Kinetics of the thermolysis of [n.2.2]propellanes and related compounds. Mechanism of the thermolysis of bicyclo[2.2.0] hexanes
Wiberg, Kenneth B.,Caringi, Joseph J.,Matturro, Michael G.
, p. 5854 - 5861 (2007/10/02)
The thermolyses of a series of 1,4-bridged bicyclo[2.2.0]hexanes have been studied. With bridges having three or more carbons, the compounds have higher activation energies than for bicyclo[2.2.0]hexane, indicating that the bridge prevents the formation of a chair cyclohexane-1,4-diyl, forcing the reaction to proceed via an orbital symmetry disallowed process. It appears likely that [2.2.2]propellane and its derivatives react via the same mechanism, and the driving force from strain relief appears to be the major factor in reducing its activation energy. The thermolysis of the relatively unstrained [3.3.2]propellane occurs at a significantly higher temperature and leads to a mixture of products which also were found in the thermolysis of 1,5-dimethylenecyclooctane. The thermolysis of the latter at 420°C formed the propellane. The strain relief in the cleavage of the central bond in this group of propellanes were estimated via a combination of ab initio and molecular mechanics calculations and was found to be correlated with the changes in activation energy. The thermolyses of [3.2.1]- and [4.2.1]propellanes also are reported and were found to be less reactive than expected on the basis of strain energy relief.
