76118-97-3Relevant academic research and scientific papers
Base Catalysed Rearrangements involving Ylide Intermediates. Part 4. Sigmatropic Rearrangements of 4-Dimethylaminobutenes and Sigmatropic Rearrangements of 3-Dimethylaminohexa-1,5-dienes
Jemison, Robert W.,Ollis, W. David,Sutherland, Ian O.,Tannock, James
, p. 1462 - 1472 (2007/10/02)
The sighmatropic rearrangement (11) -> (12) of the 9-dimethylamino-9-(1-phenylallyl)fluorene is a stereoselective process (84:16) at 170 deg C.Analogous rearrangements (16) -> (17) of the fluorene derivatives show that the reaction rate is increased by electron donating 9-substituents in the order O- > NMe2 > OMe.Similar substituent effects are observed for the Cope rearrangement (25) -> (26) of hexa-1,5-dienes. 4-Phenyl, 4,4-dimethyl, and 3-dimethylamino substituents are particularly effective in accelerating the rate of the rearrangement (25) -> (26).
