94480-80-5Relevant academic research and scientific papers
Studies on the Oxidation of cis- and trans-Pinane with Molecular Oxygen
Brose, Thomas,Pritzkow, Wilhelm,Thomas, Gerda
, p. 403 - 409 (1992)
The pinanes are preferably attacked at the tertiary C-H bond in 2-position, but products of the oxidative attack at the secondary C-H-bonds in 3- and 4-position are also found.At 100 deg C cis-pinane is attacked more easily than trans-pinane (kcis : ktrans = 6.4), the relative rates of attack at the secondary C-H bonds in positions 3 and 4 with respect to the tertiary C-H bond in 2-position were also determined (in cis-pinane ksec : ktert = 0.027; in trans-pinane ksec : ktert = 0.20).After the attack at the 2-C-H bond the radical formed can either react with oxygen to form the corresponding cis- and trans-peroxy radicals and further to give cis- and trans-2-hydroperoxy pinane or fragmentate to the monocyclic radical derived from α-terpinene, giving as a final products α-terpinene hydroperoxide and the bicyclic 8-hydroperoxy 4,4,8-trimethyl 2,3-dioxabicyclononane.The corresponding alcohols were found after reduction with sodium sulphite.The oxidation at position 2 of the pinanes delivers not only the cis- and trans-hydroperoxide but also, as short-lived intermediates, the corresponding 2-pinanyloxy radicals.These radicals fragmentate forming a carbon radical with cyclobutane structure whose oxidation products were identified.Besides fragmentation of the 2-pinanyloxy radical also an intramolecular H-transfer from the methyl group in 9-position to the oxygen of the trans-pinanyloxy radical takes place leading to 9-hydroperoxy trans-pinane-2-ol.
Lanthanide replacement in organic synthesis: Luche-type reduction of α,β-unsaturated ketones in the presence of calcium triflate
Forkel, Nina V.,Henderson, David A.,Fuchter, Matthew J.
supporting information; scheme or table, p. 2129 - 2132 (2012/09/08)
Development of a calcium-mediated regioselective 1,2-reduction of challenging α,β-unsaturated ketones, such as 2-cyclopententone, is reported. The corresponding allylic alcohols are obtained in very good regioselectivities using Ca(OTf)2 and NaBH4. Furthermore, we have shown that our method can stereoselectively reduce aziridinyl ketones.
