119182-77-3Relevant academic research and scientific papers
The Interaction of π orbitals with a carbocation over three σ bonds
Lambert, Joseph B.,Ciro, Sol M.
, p. 1940 - 1945 (2007/10/03)
The semi-π analogue of double hyperconjugation ("hyperconjugation/conjugation") has been examined in 4-isopropylidenecyclohexyl mesylate (4-OMs) by comparison with the saturated analogue, trans-4-isopropylcyclohexyl mesylate (5-OMs). The unsaturated substrate reacts in 97% trifluoroethanol only four times faster than the saturated substrate. Raber-Harris plots indicate that both substrates react by ks mechanisms; i.e., solvolysis occurs with solvent assistance rather than carbocation formation. These results are consistent with the absence of a direct, through-bond interaction of the double bond with the reactive center. The absence is caused at least in part by less than ideal overlap of the γ,δ π orbitals with the α,β σ orbitals. In contrast, an electron-rich tin atom attached to the 4-position provides a large rate enhancement and changes the mechanism to carbocation formation through double hyperconjugation.
Molecules with Twist Bent Bonds. The Synthesis, Properties, and Reactions of trans-Bicyclohept-3-ene and Certain Methylated Derivatives
Gassman, Paul G.,Bonser, Steven M.,Mlinaric-Majerski, Kata
, p. 2652 - 2662 (2007/10/02)
trans-Bicyclohept-3-ene, 7-methyl-trans-bicyclohept-3-ene, and 7,7-dimethyl-trans-bicyclohept-3-ene have been synthesized.Comparison of their ease of oxidation with the ease of oxidation of the analogous cis-bicyclohept-3-enes has been made.Both the thermal and transition-metal complex promoted rearrangements of the trans-bicyclohept-3-enes have been studied.These systems thermally convert to the cis-bicyclohept-3-enes above 100 deg C and are catalytically rearranged at ambient temperature.Trans to cis isomerization alsooccurs at ambient temperature under photoinduced single electron transfer conditions.
Molecules with Twist Bent Bonds. A Comparison of the Thermal and Transition-Metal-Complex Promoted Rearrangements of Derivatives of trans-Bicyclohept-3-ene
Gassman, Paul G.,Mlinaric-Majerski, Kata
, p. 4803 - 4806 (2007/10/02)
7-Methyl-trans-bicyclohept-3-ene has been synthesized and the thermal and transition-metal-complex promoted rearrangements of trans-bicyclohept-3-ene, 7-methyl-trans-bicyclohept-3-ene, and 7,7-dimethyl-trans-bicyclohept-3-ene have been compared.
