99646-08-9

Upstream product

• 7583-74-6 1,2-epoxy-1-t-butylcyclohexane 
• 99646-11-4 2-(1-hydroxy-1-methylethyl)-2-methylcyclohexanone 
• 186038-23-3 (1R,2R)-2-Hydroxy-1-methyl-cyclohexanecarbaldehyde 
• 1655-07-8 ethyl 2-oxocyclohexane carboxylate 
• 69551-50-4 trans-2-Hydroxymethyl-2-methyl-cyclohexanol 
• 66088-37-7 ethyl 1-methyl-2-oxocyclohexancarboxylate 

Downstream Products

• 99646-11-4 2-(1-hydroxy-1-methylethyl)-2-methylcyclohexanone 

Relevant academic research and scientific papers

Designed Chiral Acyl Radical Equivalents. Preparation and Cyclizations of Disymmetrically Substituted 1,3-Dioxabicyclo[4.4.0]decan-2-yl Radicals

The diastereoselectivity of 5-exo-trigonal cyclizations of 2-(4-penten-1-yl)-1,3-dioxolan-2-yl and 2-(4- penten-1-yl)-1,3-dioxan-2-yl radicals is investigated. When dioxolanes or dioxanes derived from C2 symmetrically substituted diols are employed the diastereoselectivity is poor. In the dioxanyl series this is a consequence of the cyclization occurring through a twist-boat conformer. Disymmetrically substituted dioxanyl radicals, derived from the alcohols 21 and 41, are, however, constrained to chairlike conformations and accordingly give rise to highly diastereoselective cyclizations. Conditions are described for the hydrolysis of the resulting spiroacetals and for determination of the ee of the resulting 2-methylcyclopentanones.

SYNTHESIS OF 1,3-DIOL DERIVATIVES FROM STERICALLY OVERCROWDED OXIRANES. RING-OPENING REACTIONS OF 1-t-BUTYL-1,2-EPOXYCYCLOHEXANE.

The acid-catalysed ring-opening reactions of 1-t-butyl-1,2-epoxycyclohexane (1) (methanolysis, hydrolysis, and trichloroacetolysis in non-protic solvents) lead to very complex mixtures.In these reactions, in addition to the non-addition products in which the t-butyl skeleton is still present, considerable amounts of other products are formed.These compounds include 1,3-secondary addition products and other rearranged non-addition products which arise by rearrangement of the original skeleton of (1), by methyl group migration; the aldehyde (20) which is lackig both the t-butyl group and the cyclohexane skeleton is also obtained.However the opening reactions of (1) in acid media are highly regioselective, most of the reaction products arising from C-O breaking on the tertiary carbon.The structures and the configurations of all the reaction products have been well established by a study of their i.r. and n.m.r. data; however, in some cases the structures and configurations were confirmed either through unequivocal syntheses and/or chemical correlations.The stereoselectivity of the trichloroacetolysis reactions of (1) is not completely anti, even if the amounts of 1,2 adducts formed are somewhat small, and the syn/anti ratio increases with the polarity of the solvent.The results obtained were rationalized through a mechanism analogous to that previously proposed for 2-aryl- and 2-ethynyl-oxiranes in which different kinds of carbenium ion species are involved.