70837-28-4Relevant academic research and scientific papers
Reaction of Azoalkanes with Isolable Cation Radical Salts
Engel, Paul S.,Robertson, Donald M.,Scholz, John N.,Shine, Henry J.
, p. 6178 - 6187 (2007/10/02)
Three tertiary azoalkanes related in the sense acyclic, cyclic, and bicyclic are shown to evolve nitrogen upon oxidation with stable cation radical salts.Thus azo-tert-octane (ATO), 3,3,6,6-tetramethyl-1,2-diazacyclohexene (TMDAC), and 1,4-dimethyl-2,3-diazabicyclooct-2-ene (Me2DBO) react rapidly with thianthrenium perchlorate (Th(.1+)ClO4(1-)), tris(p-bromophenyl)aminium hexachloroantimonate (TBPA(.1+)SbCl6(1-)), and TBPA(.1+)SbF6(1-).The ether and olefin products, which are formed in high yield in CH2Cl2/MeOH solvent, are not those expected from the usual free-radical decomposition of azoalkanes but instead implicate carbocations.Althrough the reaction stoichiometry clearly requires 2 equiv of cation radical salt to one of azoalkane, the mechanism is not yet clearly defined.A complication in these studies is found in the ability of certain cation radical salts to oxidize more azoalkane than expected based on the 2:1 stoichiometry.
66. β-Cleavage of Potassium bicyclooct-5-en-2-olates. Stereoselective Synthesis of (+-)-Trichodiene
Snowden, Roger L.,Brauchli, Robert,Sonnay, Philippe
, p. 570 - 593 (2007/10/02)
The transformation of 12 bicyclooct-5-en-2-ols (V or VI) to 3-(cyclohex-3-enyl)-2-alkanones (III or IV), via β-cleavage of their potassium alkoxides in HMPA, has been investigated (cf. table I).As an illustration of this synthetic methodology, a stereoselective synthesis of (+)-trichodiene ((+)-1) is described wich involves the β-cleavage of the tricyclic potassium alkoxides 46a and 47a to cyclopentanone 4 (cf.Scheme 7).
