61580-73-2Relevant academic research and scientific papers
GAS-PHASE ACID-INDUCED RING OPENING IN SUBSTITUTED 1,2-EPOXYCYCLOHEXANES
Crotti, Paolo,Macchia, Franco,Pizzabiocca, Adriano,Renzi, Gabriele,Speranza, Maurizio
, p. 739 - 746 (2007/10/02)
The nature and the stereoisomeric distribution of the neutral products obtained from the gas-phase attack of radiolytically formed Broensted +, CH5+, C2H5+, and t-C4H9+> and Lewis +, t-C4H9+, and CH3FCH3+> acids on several substituted 1,2-epoxycyclohexanes have been investigated under different experimental conditions.Isolation and identification of the neutral substituted products allowed us to confirm previous indications about highly regio- and stereo-selective cationic nucleophilic displacements on these substrates occuring in the gas-phase with complete inversion of the configuration at the reaction centre (the α-C atom).In some cases, extensive acid-induced isomerization became the only observable pathway.The relative extent of the competiting substitution and isomerization was found to depend on several factors, including the structural features and internal energy of the oxonium derivative of the epoxy substrate.The results obtained from the present gas-phase experiments are discussed in relation to gas-phase and solution studies.
Comparison Between the Epoxide Ring-opening of 1-Trimethylsilylcyclohexene Oxide and Some Electrophilic Additions to 1-Trimethylsilylcyclohexene
Berti, Giancarlo,Canedoli, Sergio,Crotti, Paolo,Macchia, Franco
, p. 1183 - 1188 (2007/10/02)
The reactions of 1,2-epoxy-1-trimethylsilylcyclohexane (1) with several nucleophilic reagents under acidic conditions have been studied and the ring-opened products identified.In all cases ring-opening occurs in a trans fashion with attack by the nucleoph
Some Epoxide Ring-opening Reactions of αβ-Epoxysilanes
Davis, Anthony P.,Hughes, Gwyneth J.,Lowndes, Peter R.,Robbins, Catherine M.,Thomas, Elizabeth J.,Whitham, Gordon H.
, p. 1934 - 1941 (2007/10/02)
Epoxide ring-opening of 1,2-epoxy-1-trimethylsilylcyclohexane (3) has given a range of the 2-substituted 2-trimethylsilylcyclohexanols (4; X = H, OH, OMe, OCH2CH=CH2, Br, I, SCN) in which attack by nucleophile has occured at the carbon α to silicon.The products (4) have been transformed into a number of functionalised silanes, including the silyl-episulphide (9).Other epoxides which have been less extensively studied are the conformationally biased epoxysilanes (10) and (11), the eight-membered ring epoxysilanes (17) and (21) and the two stereoisomeric 2,3-epoxy-3-trimethylsilylpentanes (26) and (29).Epoxide ring-opening adducts were obtained after treatment with H+-MeOH in all cases except for compound (17), where the bicyclic alcohol (18) was formed by a transannular reaction.
