147266-51-1

Upstream product

• 108-94-1 cyclohexanone 
• 1728-15-0 (R,S)-6-bromo-1,4-dioxaspiro<4.5>decane 
• 177-10-6 1,3-dioxolane-2-spirocyclohexane 

Downstream Products

• 1408078-65-8 2-(1-cyclohexen-1-yloxy)ethyl benzoate 
• 177-10-6 1,3-dioxolane-2-spirocyclohexane 
• 108-94-1 cyclohexanone 
• 175907-99-0 2-<<1-<(pent-4-enyl)oxy>cyclohexyl>oxy>ethanol 

Relevant academic research and scientific papers

Optimization of Grignard ring-opening of α-brominated dioxolanes for the preparation of β-hydroxy-protected vinyl ethers by a three-step one-pot procedure

Aliphatic, cyclic, and aromatic benzoate-protected γ-hydroxy enol ethers were prepared from α-brominated dioxolanes by a three-step reaction procedure and a one-pot protocol involving Grignard reagent formation, ring-opening, and final benzoate protection

Facile synthesis of enol ethers by cleavage of α-bromoacetals and α-bromoketals mediated by SmI2

α-Bromocyclicacetals, α-bromocyclicketals and α-bromocyclicthioketals, derived from cyclic and acyclic ketones and aldehydes, reacted with samarium diiodide at -78°C in THF to furnish the corresponding enol ethers or thioenol ethers containing hydroxy or thiol moieties in high yields.

5. Formation of cyclic ketals from hydroxyalkyl enol ethers, a stereoelectronically controlled endo-trig-cyclizatitm process

Acid-catalyzed cyclic ketal formation vs. hydrolysis of a series of hydroxyalkyl cyclic enol ethers in the presence of 1 equiv. of H2O, and acid-catalyzed cyclic-ketal formation (same ketals as above) vs. methanolysis of a series of mixed pent-4-enyl hydroxyalkyl ketals with N-bromosuccinimide in the presence of 4 equiv. of MeOH led to the same result: the intramolecular cyclization processes occur at similar rates as the intermolecular H2O or MeOH attacks independently of the size of the rings formed (five-, six-, or seven-niembered), by cyclizations. These results can be explained by the facts that, due to stereoelectronic effects which impose a torsional strain to the sp2 hybridized O-atom, the cyclization activation enthalpy decreases, as the length of the hydroxyalkyl chain increase (ease of cyclization: 7 > 6 > 5), whereas the entropy factor favors the cyclization in the reverse fashion (ease of cyclization: 5 > 6 > 7). The various reaction pathways have been examined using the semi-empirical Hamiltonian AM1, and the results obtained confirm that large-ring formation is enthalpically much favored over the cyclization processes leading to small rings (ease of cyclization: 7 > 6 > 5).

Oxidation of homochiral ketals by rhenium(VII) oxide. V

2-Hydroxyethyl enol ethers react with Re2O7 to produce 2-hydroxyketals. Where homochiral starting enol ethers are employed, greater than 99:1 diastereoselectivities are obtained. The stereocontrol is rationalized by invoking a transition state that approximates the geometry of a metallaoxetane. Finally, homochiral ketals are themselves oxidized to provide 2-hydroxyketals with high diastereoselectivity.