199797-26-7Relevant academic research and scientific papers
Chiral 6,7-dihydrooxepin-2(5H)-ones and the azepinone analogues: Conformation and diastereofacial selectivity in addition to the enones
Sato, Masayuki,Uehara, Fumiaki,Aizawa, Koh-Ichi,Kaneko, Chikara,Satoh, Shun-Ichi,Furuya, Toshio
, p. 633 - 636 (1996)
Diastereofacial selectivity in addition to the enones of 6- and 7-substituted dihydrooxepinones was studied. The addition occurred preferentially from the face anti to the substituent and 7-substituted substrates showed higher diastereofacial selectivity than the 6-substituted substrates. An explanation for the observed diastereofacial selectivity is proposed.
DBU-Catalyzed Deconjugation of 7-Substituted 3,4-Didehydro-2-oxepanones. Deuterium Incorporation, Significance of the Imine Double Bond, and Application to the Synthesis of a Key Pharmacophore
Jeyaraj, Duraiswamy A.,Kapoor, Kamal K.,Yadav, Veejendra K.,Gauniyal, Harsh M.,Parvez, Masood
, p. 287 - 294 (2007/10/03)
7-Substituted 3,4-Didehydro-2-oxepanones are conveniently deconjugated to the 4,5-didehydro derivatives by DBU. The isomerization of 7-benzyl-substituted 2-oxepanones proceeds to the extent of 90% over the initial 3 h; the concentration falls gradually thereafter to achieve, in 25 h, a 3:2 equilibrium in favor of deconjugation. Such an equilibrium does not exist for the 7-methyl and the 7-(2-phenethyl) derivatives. The significance of the imine double bond in DBU has been explored. The isomerization in CDCl3 causes deuterium incorporation at positions 3 and 5 of the 2-oxepanones examined and at position 6 of DBU. The mechanistic rationales for these deuterium incorporations are advanced. The transformation of 7-benzyl-3,4-didehydro-2-oxepanone into a bicyclo[3.3.0] skeleton that is present in a diverse class of biologically active natural products is described as a possible potential use of the present deconjugation methodology.
