369625-85-4Relevant academic research and scientific papers
Solvolysis of chiral cyclohexylidenemethyl triflate. Evidence against a primary vinyl cation intermediate
Fujita, Morifumi,Yamamoto, Akiyo,Sugimura, Takashi,Okuyama, Tadashi
, p. 550 - 555 (2007/10/03)
Solvolysis of (R)-4-methylcyclohexylidenemethyl triflate (6) was examined at 140°C in various aqueous methanol and some other alcoholic solvents. The main product was (R)-4-methylcycloheptanone that maintains the stereochemical purity of 6, with accompanying 4-methylcyclohexanecarbaldehyde. In the presence of bromide ion, the bromide substitution product was also obtained, mostly with inversion of configuration. It is concluded that the solvolysis does not involve the formation of the primary vinyl cation but proceeds via σ-bond participation to form the rearranged cycloheptenyl cation as an intermediate. Copyright
Solvolysis of optically active 4-methylcyclohexylidenemethyl triflate: Evidence against a primary vinyl cation as an intermediate
Fujita, Morifumi,Yamamoto, Akiyo,Sugimura, Takashi,Okuyama, Tadashi
, p. 806 - 807 (2007/10/03)
Solvolysis of (R)-4-methylcyclohexylidenemethyl triflate in aqueous methanol at 140 °C gave stereospecifically (R)-4-methylcycloheptanone to definitively rule out intermediate formation of the achiral primary vinyl cation. The rearrangement must occur via concerted σ-bond participation.
